WO2021172369A1 - Fluorine-containing polymer, film, film manufacturing method, and organic opto-electronic element - Google Patents

Fluorine-containing polymer, film, film manufacturing method, and organic opto-electronic element Download PDF

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WO2021172369A1
WO2021172369A1 PCT/JP2021/006902 JP2021006902W WO2021172369A1 WO 2021172369 A1 WO2021172369 A1 WO 2021172369A1 JP 2021006902 W JP2021006902 W JP 2021006902W WO 2021172369 A1 WO2021172369 A1 WO 2021172369A1
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fluorine
containing polymer
film
temperature
organic
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PCT/JP2021/006902
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French (fr)
Japanese (ja)
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岳文 阿部
薫 鶴岡
下平　哲司
早希 中村
祥太朗 別府
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Ａｇｃ株式会社
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Priority to JP2022503657A priority Critical patent/JPWO2021172369A1/ja
Priority to CN202180017316.XA priority patent/CN115175947A/en
Priority to KR1020227027079A priority patent/KR20220147075A/en
Priority to EP21761065.8A priority patent/EP4112655A1/en
Publication of WO2021172369A1 publication Critical patent/WO2021172369A1/en
Priority to US17/817,132 priority patent/US20220372186A1/en

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/16—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering
    • H10K71/164—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering using vacuum deposition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C08F214/26—Tetrafluoroethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C08F214/26—Tetrafluoroethene
    • C08F214/262—Tetrafluoroethene with fluorinated vinyl ethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/14—Esterification
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/18—Introducing halogen atoms or halogen-containing groups
    • C08F8/20—Halogenation
    • C08F8/22—Halogenation by reaction with free halogens
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/22—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers modified by chemical after-treatment
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/115—Polyfluorene; Derivatives thereof
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/17—Carrier injection layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/85—Arrangements for extracting light from the devices
    • H10K50/858—Arrangements for extracting light from the devices comprising refractive means, e.g. lenses
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a fluorine-containing polymer, a film, a method for producing a film, and an organic photoelectron device.
  • an organic photoelectron element organic electroluminescence element, hereinafter referred to as an organic EL element
  • a self-luminous element organic photoelectron element
  • the basic structure of an organic EL element is such that a plurality of types of layers such as a light emitting layer, an electron transporting layer, and a hole transporting layer are laminated between a pair of electrodes.
  • Fluororesin may be used as a material for a plurality of types of layers constituting an organic EL element. Fluororesin is used for various purposes such as a low refractive index material for lowering the refractive index of a layer and a buffer for an electrode.
  • an organic EL device having an anode buffer layer made of a fluororesin is known (see Patent Document 1). In the organic EL device described in Patent Document 1, an anode buffer layer is formed by depositing a fluororesin.
  • Patent Document 1 it is described that the fluororesin is vapor-deposited under reduced pressure in a vacuum chamber.
  • the pressure in the chamber which was 8 ⁇ 10 -3 Pa at the start of film formation, has increased to 1 to 3 ⁇ 10 -2 Pa at the end of film formation. It is considered that this is because the fluororesin used is thermally decomposed under the vapor deposition conditions, and the generated small molecule decomposition products are vaporized to increase the pressure in the chamber.
  • Patent Document 1 when a fluororesin that thermally decomposes during vapor deposition is used, it is expected that it is difficult to secure desired vapor deposition conditions. Therefore, even if an organic EL element is obtained, the quality may not be stable, and improvement has been required.
  • the present invention has been made in view of such circumstances, and an object of the present invention is to provide a fluorine-containing polymer suitable for vapor deposition. Another object of the present invention is to provide a film containing such a fluorine-containing polymer as a material. Another object of the present invention is to provide a method for producing a film capable of easily producing such a film. Another object of the present invention is to provide an organic photoelectron element having such a film in its structure.
  • a fluorine-containing polymer that satisfies the following (1) to (3).
  • the melting point is 200 ° C. or higher.
  • the thermogravimetric reduction rate when the temperature is raised at a heating rate of 2 ° C./min under a pressure of 1 ⁇ 10 -3 Pa reaches substantially 100% at 400 ° C. or lower.
  • the temperature range from the temperature at which the thermogravimetric reduction rate is 10% to the temperature at which the temperature is 90% is 100 ° C.
  • [7] A film containing the fluorine-containing polymer according to any one of [1] to [6] and an organic semiconductor.
  • [8] The film according to [7], wherein the ratio of the fluorine-containing polymer to the total of the fluorine-containing polymer and the organic semiconductor is 20 to 80% by volume.
  • a method for producing a film which comprises a step of co-depositing the fluorine-containing polymer according to any one of [1] to [6] and an organic semiconductor.
  • An organic photoelectron device including the film according to any one of [7] to [10].
  • the hole transport layer and the hole injection layer arranged between the hole transport layer and the anode are provided, and at least one layer of the hole transport layer and the hole injection layer is said.
  • the organic photoelectron element according to [13] which is a film.
  • the electron transport layer and the electron injection layer arranged between the electron transport layer and the cathode are provided, and at least one layer of the electron transport layer and the electron injection layer is the film. 13] or the organic photoelectron element according to [14].
  • a fluorine-containing polymer suitable for vapor deposition it is possible to provide a film containing such a fluorine-containing polymer as a material. Further, it is possible to provide a method for producing a film capable of easily producing such a film. Further, it is possible to provide an organic photoelectron element having such a film in its structure.
  • FIG. 1 is a schematic diagram illustrating the requirements (2) and (3) of the fluorine-containing polymer.
  • FIG. 2 is a schematic cross-sectional view showing the film of the first embodiment.
  • FIG. 3 is a schematic view showing a process of manufacturing the film 10.
  • FIG. 4 is a schematic view showing a process of manufacturing the film 10.
  • FIG. 5 is a schematic view showing a process of manufacturing the film 10.
  • FIG. 6 is a schematic cross-sectional view showing an organic photoelectronic device (organic EL device) 100 according to a second embodiment of the present invention.
  • FIG. 7 is an explanatory diagram of the organic EL element 200 according to the third embodiment of the present invention.
  • the "unit" constituting the polymer in the present specification means a portion derived from one monomer molecule (that is, a monomer unit) that exists in the polymer and constitutes the polymer.
  • a unit derived from an individual monomer may be referred to by adding a "unit" to the monomer name.
  • the "main chain" of the polymer constitutes a carbon-carbon unsaturated double bond in the monomer generated by addition polymerization of the monomer having a carbon-carbon unsaturated double bond.
  • the "aliphatic ring" in the present specification includes not only a carbocyclic ring structure in which the ring skeleton is composed of only carbon atoms, but also a heterocyclic ring structure in which the ring skeleton contains atoms other than carbon atoms (heteroatoms). means.
  • the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom and the like.
  • the fluorine-containing polymer of the present embodiment satisfies the following requirements (1) to (3).
  • Requirements (1) The melting point is 200 ° C or higher.
  • Requirement (2) The thermogravimetric reduction rate when the temperature is raised at a heating rate of 2 ° C./min under a pressure of 1 ⁇ 10 -3 Pa reaches substantially 100% at 400 ° C. or lower.
  • Requirement (3) When the temperature is raised at a heating rate of 2 ° C./min under a pressure of 1 ⁇ 10 -3 Pa, the temperature range from the temperature at which the thermogravimetric reduction rate becomes 10% to the temperature at which the temperature decreases to 90% is 100. It is within ° C.
  • Fluorine-containing polymers that satisfy the above requirements (1) to (3) have physical properties suitable for vapor deposition, and a vapor-deposited film can be suitably formed. Hereinafter, they will be described in order.
  • the unit of the fluorine-containing polymer of the present embodiment is not particularly limited as long as it has high crystallinity and a melting point in a desired range.
  • the fluorine-containing polymer is preferably a polymer having a unit derived from a fluoroolefin. More specifically, the fluorine-containing polymer preferably has at least a unit derived from tetrafluoroethylene (TFE) (that is, a TFE unit).
  • TFE tetrafluoroethylene
  • a fluorine-containing polymer can obtain high crystallinity when it contains a TFE unit or a unit derived from chlorotrifluoroethylene (CTFE) (that is, a CTFE unit) in a high ratio. Therefore, it is preferable that the fluorine-containing polymer of the present embodiment also contains TFE units and CTFE units in a high ratio.
  • CTFE chlorotrifluoroethylene
  • the ratio of the TFE unit and the CTFE unit to the entire fluorine-containing polymer is preferably 50 mol% or more, more preferably 70 mol% or more, and further preferably 90 mol% or more.
  • the fluorine-containing polymer contains both TFE units and CTFE units, it is preferable that the sum of the ratio of TFE units and the ratio of CTFE units is equal to or greater than the above-mentioned content ratio.
  • the upper limit of the content rate is 100 mol%.
  • the fluoropolymer of the present embodiment may be a homopolymer of TFE or CTFE, and is a copolymer of two or more kinds of monomers selected from the group consisting of TFE or CTFE and other monomers. May be good.
  • the other monomer is not particularly limited as long as it can be copolymerized with TFE or CTFE.
  • the other monomer may be a hydrocarbon-based monomer or a fluorine-containing monomer.
  • hydrocarbon-based monomer examples include hydrocarbon-based monomers such as ethylene, propylene, and styrene.
  • hydrocarbon-based monomers such as ethylene, propylene, and styrene.
  • the ratio of the units derived from the other monomer to all the units of the fluorine-containing polymer is preferably 50 mol% or less, preferably 30 mol% or less. Is more preferable, and 10 mol% or less is further preferable.
  • the fluorine-containing monomer is preferable as the other monomer.
  • a perfluoro compound is preferable.
  • the fluorine-containing monomer which is another monomer, may be a monomer that becomes a unit having an aliphatic ring structure in the main chain by polymerization, but the main chain of such a fluorine-containing polymer may be used. It is preferably not a monomer that provides an aliphatic ring structure.
  • the fluorinated polymer having no aliphatic ring structure in the main chain has higher crystallinity than the fluorinated polymer having an aliphatic ring structure in the main chain, and the melting point of the fluorinated polymer is controlled within a desired range. It's easy to do.
  • Examples of the monomer that becomes a unit having an aliphatic ring structure in the main chain by polymerization include perfluorocyclic monoene and perfluorodiene that can be cyclized and polymerized, which will be described later.
  • Examples of the fluorine-containing monomer other than the perfluoro compound include trifluoroethylene (TrFE), vinylidene fluoride (VdF), 1,2-difluoroethylene, 1-fluoroethylene and the like.
  • perfluoro compound among the fluorine-containing monomers examples include the following perfluoroolefins, perfluoroalkyl vinyl ethers, perfluorocyclic monoenes, perfluorodienes capable of cyclization polymerization, and the like.
  • Perfluoroolefin hexafluoropropene (HFP), etc.
  • Perfluoroalkyl vinyl ether perfluoromethyl vinyl ether (PMVE), perfluoroethyl vinyl ether (PEVE), perfluoropropyl vinyl ether (PPVE), etc.
  • Perfluorocyclic monoene perfluoro (4-methoxy-1,3-dioxol) ), Perfluoro (2,2-dimethyl-1,3-dioxol), Perfluoro (4-methyl-2-methylene-1,3-dioxolane), etc.
  • Perfluorodiene capable of cyclization polymerization Perfluoro (3-butenyl vinyl ether) etc
  • the fluorine-containing polymer preferably has a perfluoroalkyl vinyl ether unit.
  • the fluorine-containing polymer preferably has PPVE units.
  • the melting point of the fluorine-containing polymer changes when the content of PPVE units changes. Specifically, as the content of PPVE units with respect to the fluorine-containing polymer increases, the melting point of the fluorine-containing polymer tends to decrease.
  • the content of PPVE units with respect to the fluorine-containing polymer is preferably less than 14 mol%, more preferably 10 mol% or less.
  • the upper limit of the content of PPVE units with respect to the fluorine-containing polymer is not particularly limited, but is preferably more than 0 mol%, more preferably 1 mol% or more.
  • the upper limit value and the lower limit value can be arbitrarily combined.
  • the content is preferably 1 to 12 mol%.
  • Each of the above-mentioned monomers is usually polymerized by radical polymerization using a radical polymerization initiator.
  • the structure at the end of the molecular chain (main chain) of the fluoropolymer at the end of polymerization is a structure to which a fragment of the radical polymerization initiator used in the polymerization is added.
  • the structure at the end of the molecular chain (main chain) can be a structure to which a fragment of the chain transfer agent is added.
  • the terminal structure may be converted into another structure.
  • the structure at the end of the main chain becomes a methyl ester group.
  • the methyl ester group can be converted from a highly reactive acid fluoride by a simple methanol treatment. Therefore, it is preferable because the stability of the obtained fluorine-containing polymer can be easily improved.
  • the structure at the end of the main chain becomes a trifluoromethyl group.
  • the fluorination treatment include the treatment method described in paragraph 0040 of JP-A-11-152310.
  • the trifluoromethyl group is preferable because it has high heat resistance and the heat resistance of the obtained fluorine-containing polymer can be easily improved.
  • the fluorine-containing polymer when the structure at the end of the main chain is a methyl ester group or a trifluoromethyl group, the intermolecular interaction at the end of the main chain is small and vapor deposition is easy, which is preferable.
  • the structure at the end of the main chain described above can be confirmed by infrared spectroscopic analysis.
  • the fluorine-containing polymer of the present embodiment preferably has crystallinity. Since the fluorine-containing polymer has crystallinity, the melting point tends to be 200 ° C. or higher.
  • the melting point of the fluorine-containing polymer of the present embodiment is preferably 215 ° C. or higher, more preferably 225 ° C. or higher, and even more preferably 240 ° C. or higher.
  • the upper limit of the melting point of the fluorine-containing polymer of the present embodiment is not particularly limited, but is preferably 350 ° C. or lower, more preferably 320 ° C. or lower, and even more preferably 300 ° C. or lower.
  • the upper limit value and the lower limit value of the melting point of the fluorine-containing polymer can be arbitrarily combined.
  • the melting point of the fluorine-containing polymer may be 200 to 350 ° C., 215 to 320 ° C., or 225 to 300 ° C.
  • the melting point adopts a value measured using a differential scanning calorimeter (for example, manufactured by NETZSCH: DSC 204 F1 Phoenix). 9 mg of the fluorine-containing polymer is charged in a sample container, the heat capacity when the temperature is raised from ⁇ 70 ° C. to 350 at 10 ° C. per minute is measured, and the melting point is determined from the obtained melting peak.
  • a differential scanning calorimeter for example, manufactured by NETZSCH: DSC 204 F1 Phoenix.
  • thermogravimetric reduction rate adopts a value measured using a vacuum differential thermal balance (manufactured by Advance Riko Co., Ltd .: VPE-9000). Specifically, the fluorine-containing weight when 50 mg of the fluorine-containing polymer was charged into a cell having an inner diameter of 7 mm and the temperature was raised from room temperature to 500 ° C. at 2 ° C. per minute at a vacuum degree of 1 ⁇ 10 -3 Pa. The weight loss rate (%) with respect to the initial weight (50 mg) of the coalescence is measured.
  • “Substantially” in the requirement (2) means that in the above-mentioned method for measuring the thermogravimetric rate, the thermogravimetric decrease in the temperature range exceeding 400 ° C. is below the lower limit of detection, and the thermogravimetric decrease cannot be confirmed. Means that.
  • the fluorinated polymer of the present embodiment satisfies the above requirement (2), the lower the molecular weight (degree of polymerization). If an attempt is made to heat a fluorinated polymer that does not satisfy the above requirement (2) in a temperature range exceeding 400 ° C., the fluorinated polymer may be thermally decomposed. In that case, the product produced by thermal decomposition may increase the internal pressure of the vacuum chamber used for vapor deposition. When the internal pressure of the vacuum chamber rises in this way, the vapor deposition conditions become unstable, and the quality of the vapor deposition film may not be stable. In addition, the partially thermally decomposed fluorine-containing polymer may be mixed in the vapor-deposited film, and the quality of the vapor-deposited film may be impaired.
  • the fluorine-containing polymer satisfying the above requirement (2) when used as a vapor deposition material performed under vacuum, it can be suitably vapor-deposited by heating at a temperature lower than 400 ° C. As a result, there is no risk of thermal decomposition described above, and the vapor deposition process can be performed under stable vapor deposition conditions.
  • the heat resistance of the fluorine-containing polymer can be evaluated as follows, focusing on the change in the internal pressure of the vacuum chamber.
  • a fluorine-containing polymer having an increase ratio of more than 2 times is likely to undergo thermal decomposition and can be judged to be unsuitable for use in vapor deposition. Further, when the fluorine-containing polymer is thermally decomposed so that the increase ratio of the chamber pressure exceeds 10 times, the quality of the vapor-deposited film to be produced may not be stable due to the product produced by the thermal decomposition.
  • the fluorine-containing polymer of the present embodiment has a thermogravimetric reduction rate of substantially 100% at 350 ° C. or lower when the temperature is raised at a heating rate of 2 ° C./min under a pressure of 1 ⁇ 10 -3 Pa. It is preferable to reach.
  • the fluorine-containing polymer of the present embodiment has a temperature at which the thermogravimetric reduction rate changes from 10% to 90% when the temperature is raised at a temperature rising rate of 2 ° C./min under a pressure of 1 ⁇ 10 -3 Pa.
  • the temperature range up to is within 100 ° C.
  • the fluorinated polymer of the present embodiment has a narrower molecular weight distribution as the temperature range satisfying the above requirement (3) is narrower.
  • the molecular weight of the fluorine-containing polymer deposited at the beginning of vapor deposition and the molecular weight of the fluorine-containing polymer deposited at the end of vapor deposition In the same vapor-deposited film, the molecular weight of the fluorine-containing polymer changes in the thickness direction of the thin-film film, and the physical properties of the thin-film film may not be stable.
  • the quality of the produced film-deposited film may vary from lot to lot. If a fluorine-containing polymer that does not satisfy the requirement (3) is used as described above, the vapor deposition conditions may become unstable and the quality of the vapor deposition film may not be stable.
  • the difference between the molecular weight of the fluorine-containing polymer deposited at the beginning of vapor deposition and the molecular weight of the fluorine-containing polymer deposited at the end of vapor deposition is small, and the vapor deposition is carried out.
  • the change in the molecular weight of the fluorine-containing polymer is small in the thickness direction of the film. Therefore, the physical characteristics of the obtained thin-film film are likely to be stable.
  • the vapor-deposited film is continuously produced under the same conditions, it is possible to suppress quality variation between lots of the produced vapor-film film. Therefore, when a fluorine-containing polymer satisfying the requirement (3) is used, the quality of the vapor-deposited film is likely to be stable.
  • the fluorine-containing polymer of the present embodiment has a temperature at which the thermogravimetric reduction rate changes from 10% to 90% when the temperature is raised at a temperature rising rate of 2 ° C./min under a pressure of 1 ⁇ 10 -3 Pa.
  • the temperature range up to is preferably 70 ° C. or less.
  • FIG. 1 is a schematic diagram for explaining the requirements (2) and (3), and is a graph showing the correspondence relationship between the thermogravimetric reduction rate and the measured temperature.
  • the horizontal axis of FIG. 1 is the measurement temperature (unit: ° C.), and the vertical axis is the thermogravimetric reduction rate (unit:%).
  • the behavior of the fluorinated polymer satisfying the requirements (2) and (3) is indicated by reference numeral P
  • the behavior of the fluorinated polymer not satisfying the requirements (2) and (3) is indicated by reference numeral Px.
  • the graph P showing the behavior of the fluorine-containing polymer of the present embodiment shows that the thermogravimetric reduction rate reaches 100% at a temperature (T d100) lower than 400 ° C.
  • the thermogravimetric reduction rate does not reach 100% at 400 ° C.
  • the value W of T d90- T d10 is 100 ° C. or less. From FIG. 1, it can be seen that the fluorine-containing polymer of the present embodiment causes a sharp decrease in thermogravimetric analysis between the temperature T d10 and the temperature T d90.
  • a fluorine-containing polymer satisfying the above requirements (2) and (3) can be obtained by fractionating the molecular weight of the polymer.
  • the polymer subject to molecular weight fractionation may be referred to as a "raw material polymer”.
  • Examples of the method of molecular weight fractionation include a method of fractionating the molecular weight by sublimation purification or supercritical extraction to prepare a polymer satisfying the requirements (2) and (3).
  • sublimation purification In sublimation purification, the purification target (raw material polymer) is heated under reduced pressure to sublimate or evaporate a part or all of the purification target, and then the precipitation temperature difference of the compound contained in the purification target in a gaseous state is measured. This is a method for separating and recovering a target compound as a solid.
  • Such sublimation purification has a charging section for charging the object to be purified and a collecting section for separating the purified object in a gaseous state at each precipitation temperature and collecting it as a solid, and maintains a high degree of vacuum. It can be carried out using a sublimation purification apparatus capable of this.
  • the structure of the sublimation purification device is not particularly limited, but for example, a so-called Mill-type sublimation purification device consisting of a glass cooling tube, a flask-shaped glass container surrounding the cooling tube, and a vacuum exhaust device for depressurizing the inside of the glass container.
  • the sublimation refining device includes a cylindrical glass sublimation tube, a heating device that houses the sublimation tube inside to heat the sublimation tube, and a high vacuum exhaust device that depressurizes the inside of the sublimation tube.
  • a glass tube type sublimation purification device can also be used.
  • a method for sublimation purification of a fluorine-containing polymer and a method for fractionating the molecular weight by sublimation purification will be described using a glass tube type sublimation purification apparatus as an example.
  • the raw material polymer is charged in the preparation part of the sublimation tube, and the vacuum degree in the sublimation tube is raised to, for example, 1 ⁇ 10 -3 Pa or less by using a high vacuum exhaust device.
  • the preparation part is heated using a heating device.
  • the fluorine-containing polymer contained in the raw material polymer is sublimated or evaporated.
  • the area corresponding to the exhaust side of the high vacuum exhaust device from the preparation part corresponds to the "collection part".
  • the collecting part is set to a temperature lower than the heating temperature of the charging part.
  • the fluorine-containing polymer sublimated or evaporated from the raw material polymer in the charging section is precipitated and solidified on the wall surface of the collecting section and collected.
  • the collection temperature of the collection unit corresponds to the temperature at which the fluorine-containing polymer sublimates from a gas to a solid (the temperature at which it precipitates), and corresponds to the molecular weight of the fluorine-containing polymer.
  • the raw material polymer can be fractionated into fluorine-containing polymers having different molecular weights. For example, specifically, when the charging portion is heated to A ° C. and the collecting portion is heated to B ° C. and C ° C. from the side closer to the charging portion (A>B> C), the trapping portion is set to B ° C.
  • a fluorine-containing polymer having a molecular weight range that becomes a gas at A ° C and a solid at B ° C is collected.
  • a fluorine-containing polymer in a molecular weight range that becomes a gas at B ° C and a solid at C ° C is collected. That is, in the collection section set to C ° C., among the fluorine-containing polymers contained in the raw material polymer, the fluorine-containing weight having a collection temperature range of B ° C.—C ° C. which is a gas at B ° C. and a solid at C ° C. The coalescence is collected.
  • the above-mentioned requirement (3) can be satisfied by controlling the collection temperature range as described above, for example, by collecting in a collection section having a collection temperature range of 100 ° C. It should be noted that it is confirmed whether or not the collected fluorine-containing polymer satisfies the requirement (3), and if the requirement (3) is not satisfied, the temperature condition of the collecting portion is controlled and the collecting temperature range is adjusted. It is good to narrow it.
  • the fluorine-containing polymer collected in the lower set temperature region has a lower temperature at which the thermogravimetric reduction rate reaches 100% under a pressure of 1 ⁇ 10 -3 Pa, that is, has a smaller molecular weight. It becomes a polymer.
  • the collection temperature range is preferably 100 ° C. or lower, more preferably 70 ° C. or lower, and even more preferably 40 ° C. or lower.
  • the smaller the collection temperature range the less the fluctuation of the vapor deposition conditions, and the more likely it is that a homogeneous phase-separated structure is formed in the film thickness direction.
  • the fluorinated polymer fractionated by molecular weight may be a mixture of a plurality of fluorinated polymers having different collection temperature ranges as long as the requirements (2) and (3) are satisfied.
  • Supercritical extraction is a technique for obtaining an extract by utilizing the high solubility and diffusivity of a supercritical fluid.
  • supercritical extraction for example, supercritical CO 2 is used as a supercritical fluid, and a fluorine-containing polymer having a relatively low molecular weight is dissolved in the supercritical CO 2 to obtain an extract.
  • a fluorine-containing solvent as an additive (entrainer) for the supercritical fluid, the solubility of the fluorine-containing polymer in the supercritical fluid can be enhanced.
  • the fluorine-containing solvent used as the entrainer is not particularly limited.
  • a fluorinated solvent is preferred
  • Fluorophilic parameter P F calculated by the following method is one or more. (Parent fluorine parameter P F) 30 ⁇ L of the fluorine-containing solvent was added dropwise to a two-phase system of 3 g of toluene and 3 g of perfluoromethylcyclohexane, mixed well and allowed to stand overnight, and then the fluorine-containing solvent contained in the toluene and the perfluoromethyl were added. The fluorine-containing solvent contained in cyclohexane is measured by gas chromatography.
  • the extraction step can be carried out using, for example, supercritical CO 2 under the conditions of an extraction pressure of 7.4 MPa or more and an extraction temperature of 31 ° C. or more.
  • the extraction pressure is preferably 30 MPa or more, more preferably 50 MPa or more, and even more preferably 70 MPa or more.
  • the upper limit of the extraction pressure is not particularly limited, but is preferably 100 MPa or less.
  • the upper limit value and the lower limit value of the extraction pressure can be arbitrarily combined.
  • the extraction temperature is preferably 40 ° C. or higher, more preferably 80 ° C. or higher.
  • the extraction temperature is preferably 300 ° C. or lower, more preferably 200 ° C. or lower, and even more preferably 100 ° C. or lower.
  • the upper limit value and the lower limit value of the extraction temperature can be arbitrarily combined. Within the above range, the molecular weight fractionation of the target fluorine-containing polymer can be efficiently performed.
  • the fluorine-containing polymer of the present embodiment preferably satisfies the following requirements (4) and (5).
  • Requirement (4) a storage modulus at 25 ° C. is 1 ⁇ 10 7 Pa or higher.
  • Requirement (5) When the fluorine-containing polymer is cooled at a temperature lowering rate of 2 ° C./min, the temperature at which the storage elastic modulus is less than 1 ⁇ 10 6 Pa is 120 ° C. or higher.
  • the fluorine-containing polymer satisfies the above requirements (4) and (5), the heat resistance of the fluorine-containing polymer becomes high.
  • the fluorine-containing polymer satisfying the above requirements (4) and (5) can be obtained, for example, by changing the content rate of the PPVE unit contained in the fluorine-containing polymer. As the content of PPVE units increases, the storage elastic modulus tends to decrease.
  • the storage elastic modulus is measured using a dynamic viscoelasticity measuring device (for example, Anton Pearl Co., Ltd., MCR502) and a heating furnace for a viscoelasticity measuring device (for example, Anton Pearl Co., Ltd., CTD450).
  • Adopt a value Specifically, after heating the sample (fluorine-containing polymer) to a melting point or higher, the temperature is lowered at 2 ° C./min in the constant-speed temperature lowering mode.
  • the storage elastic modulus (G') is measured under the conditions of a strain of 0.01% and a frequency of 1 Hz.
  • FIG. 2 is a schematic cross-sectional view showing the film of the present embodiment.
  • the film 10 shown in FIG. 2 is a co-deposited film of an organic semiconductor and a fluorine-containing polymer, and is formed on the substrate 50.
  • the organic semiconductor and the fluorine-containing polymer are phase-separated, and include the domain 51b of the organic semiconductor and the domain 52b of the fluorine-containing polymer described above.
  • the domain 51b and the domain 52b are continuous in the film thickness direction.
  • the size D of the domain 52b in the plane direction of the film 10 is, for example, about 10 nm to 20 nm.
  • the above-mentioned phase-separated structure of the membrane 10 may be referred to as a nanodomain structure.
  • the fluorine-containing polymer used in the present embodiment has a melting point of 200 ° C. or higher and has high crystallinity.
  • a film having high heat resistance can be obtained.
  • a film formed by using a material having high crystallinity tends to have a high haze and low transparency because the crystallized portion scatters visible light. For this reason, it has been difficult to apply a film formed using a material having high crystallinity to a photoelectron device or the like that requires transparency.
  • the film 10 has a nanodomain structure that is sufficiently small with respect to visible light. Even if a part of the fluorine-containing polymer contained in such a film 10 is crystallized, the size of the crystallized part is a size that fits in the nanodomain structure. Therefore, the film 10 is less likely to scatter visible light and exhibits high transparency. Further, the film 10 has high heat resistance based on the high crystallinity of the fluorine-containing polymer. Therefore, the film 10 retains the nanodomain structure even when exposed to a high temperature, and can maintain high transparency.
  • the haze of the film 10 and its heat resistance can be measured by the following method.
  • ⁇ -NPD and a fluorine-containing polymer are co-deposited on a glass substrate to form a 100 nm co-deposited film to obtain a sample for haze measurement.
  • the total deposition rate of the two materials is 0.2 nm / sec.
  • the vapor deposition rate is adjusted so that the volume ratio of ⁇ -NPD to the fluorine-containing polymer in the co-deposited film is a desired ratio.
  • Haze measurement is performed using a haze meter (Haze Guard K50-290 manufactured by Toyo Seiki Co., Ltd.). After measuring the initial haze of the haze measurement sample, the sample sample is heated on a hot plate heated to 100 ° C. for 1 hour. After returning the sample to room temperature, measure the haze again. Further, the sample is heated on a hot plate heated to 120 ° C. for 1 hour, and the haze is measured in the same manner.
  • a haze meter Haze Guard K50-290 manufactured by Toyo Seiki Co., Ltd.
  • the obtained haze is evaluated as follows. ⁇ : Less than 0.2, ⁇ : 0.2 or more and less than 0.5 ⁇ : 0.5 or more
  • the ratio of the fluorinated polymer to the total of the fluorinated polymer constituting the film 10 and the organic semiconductor is equal to the volume of the domain 52b with respect to the entire film 10.
  • the ratio of the domain 52b to the entire membrane 10 is preferably 20 to 80% by volume.
  • the proportion of the fluorine-containing polymer is 20% by volume or more, the film has a sufficiently low refractive index as compared with the film of the organic semiconductor having no fluorine-containing polymer. Further, when the proportion of the fluorine-containing polymer is 80% by volume or less, the conductivity of the film 10 can be sufficiently ensured.
  • the refractive index of the film 10 can be measured by the following method using a sample prepared by the following method.
  • ⁇ -NPD and a fluorine-containing polymer are co-deposited on a silicon substrate to form a 100 nm co-deposited film to obtain a sample for refractive index measurement.
  • the total deposition rate of the two materials is 0.2 nm / sec.
  • the vapor deposition rate is adjusted so that the volume ratio of ⁇ -NPD to the fluorine-containing polymer in the co-deposited film is a desired ratio.
  • the organic semiconductor includes a hole injection material that constitutes a hole injection layer of an organic EL device, an electron injection material that constitutes an electron injection layer, a hole transport material that constitutes a hole transport layer, and an electron transport layer.
  • the organic semiconductor includes a hole injection material that constitutes a hole injection layer of an organic EL device, an electron injection material that constitutes an electron injection layer, a hole transport material that constitutes a hole transport layer, and an electron transport layer. Examples of electron transport materials, host materials and guest materials constituting the light emitting layer can be exemplified.
  • an aromatic amine derivative can be preferably exemplified. Specific examples include, but are not limited to, the following ⁇ -NPD, TAPC, PDA, TPD, m-MTDATA, and the like.
  • Examples of the hole injection material other than the above include the following semiconductor materials, organometallic complex materials, arylamine materials, polymer semiconductor materials, and the like.
  • Semiconductor materials Metal oxides such as molybdenum oxide and tungsten oxide, metal fluorides such as aluminum fluoride and magnesium fluoride
  • Organic metal complex materials Copper phthalocyanines, etc.
  • Aarylamine materials N, N'-diphenyl-N, N'- Bis- [4- (phenyl-m-tolyl-amino) -phenyl] -biphenyl-4,4'-diamine (DNTPD), N, N'-di (1-naphthyl) -N, N'-diphenylbenzidine ( NPB), 4,4', 4 "-tris (N, N-diphenylamino) triphenylamine (TDATA), dipyrazino [2,3-f: 2', 3'-h] quinoxalin-2,3,6 , 7,10,11-Hexacarbonitrile (HAT-CN), 9,9', 9 "-triphenyl-9H, 9'H, 9"H-3,3':6', 3 "-tercarbazole (Tris-PCz), 4,4', 4 "-Tris (N, N-2-naphthylphenylamino) Triphenylamine (2
  • Polymer semiconductor materials Polyaniline / dodecylbenzenesulfonic acid (PANI / DBSA) ), Poly (3,4-ethylenedioxythiophene) / Poly (4-styrenesulfonate) (PEDOT / PSS), Polyaniline camphorsulfonic acid (PANI / CSA), or Polyaniline / Poly (4-styrenesulfonate) (PANI / PSS) etc.
  • PANI / DBSA Polyaniline / dodecylbenzenesulfonic acid
  • PEDOT / PSS Poly (3,4-ethylenedioxythiophene) / Poly (4-styrenesulfonate)
  • PANI / CSA Polyaniline camphorsulfonic acid
  • PANI / PSS Polyaniline / Poly (4-styrenesulfonate
  • N- (diphenyl-4-yl) -9,9-dimethyl-N- (4- (9-phenyl-9H-carbazoyl-3yl) phenyl) -9H-fluoren-2-amine hereinafter referred to as "HT211"
  • HTM081 manufactured by Merck
  • HTM163 manufactured by Merck
  • HTM222 manufactured by Merck
  • NHT-5 manufactured by NoValed
  • NHT-18 manufactured by NoValed
  • NHT- 49 manufactured by NoValed
  • NHT-51 manufactured by NoValed
  • NDP-2 manufactured by NoValed
  • NDP-9 manufactured by NoValed
  • the hole injection material illustrated can be purchased commercially. As these hole injection materials, commercially available products or synthetic products may be used. Further, the hole injection material may be used alone or in combination of two or more.
  • the electron injection material a known material can be used. Specific examples include inorganic compounds such as LiF, Cs 2 CO 3 , CsF, and the following Alq 3 , PBD, TAZ, BND, OXD-7, 8-hydroxyquinolinolato-lithium (Liq), and the like. , Not limited to these. In addition, commercially available products such as NDN-1 (manufactured by NoValed) and NDN-26 (manufactured by NoValed) can be used.
  • NDN-1 manufactured by NoValed
  • NDN-26 manufactured by NoValed
  • Examples of the material of the hole transport layer include, but are not limited to, the hole injection material.
  • the hole injection material 4,4', 4 "-tri (9-carbazoyl) trifemilamine (TCTA), 2,2', 7,7'-tetrakis (N, N) other than those listed as the hole injection materials.
  • TCTA 4,4', 4 "-tri (9-carbazoyl) trifemilamine
  • N, N 2,2', 7,7'-tetrakis
  • Arylamine materials such as 9,9'-spirobifluorene (Spiro-MeOTAD) can be used as the hole transport material.
  • Hole-transporting materials other than those listed as the hole-injecting materials include triazole derivatives, oxadiazole derivatives, imidazole derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, and oxazole derivatives. , Styrylanthracene derivative, fluorenone derivative, hydrazone derivative, stilben derivative, silazane derivative and the like. Among them, it is preferable to use a porphyrin compound, an aromatic tertiary amine compound and a styrylamine compound, particularly an aromatic tertiary amine compound. As these hole transporting materials, commercially available products or synthetic products may be used. Further, the hole transporting material may be used alone or in combination of two or more.
  • the electron transport material As the material of the electron transport layer (electron transport material), a known material can be used.
  • the electron transport material includes, but is not limited to, the electron injection material.
  • Examples of the electron transporting material other than those listed as the electron injecting material include 2,2', 2''-(1,3,5-benzinetriyl) -tris (1-phenyl-1-H-benzimidazole).
  • TPBi 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline
  • BCP 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline
  • BCP 2- (4-tert-butylphenyl) -5- (4-biphenylyl) -1,3,4-
  • oxadiazole t-Bu-PBD
  • silol derivative having a silol ring.
  • electron transport materials commercially available products or synthetic products may be used. Further, the electron transport material may be used alone or in combination of two or more.
  • the material for forming the light emitting layer known materials such as a fluorescent material, a thermal activated delayed fluorescence (TADF) material, and a phosphorescent material can be adopted.
  • TADF thermal activated delayed fluorescence
  • examples of the material for forming the light emitting layer include (E) -2- (2- (4- (dimethylamino) styryl) -6-methyl-4H-pyran-4-iriden) malononitrile (DCM) and 4- (dicyano).
  • Luminescent guest materials such as methylene) -2-methyl-6-juloridyl-9-enyl-4H-pyran (DCM 2 ), rubrene, polymer6, Ir (ppy) 3 , (ppy) 2 Ir (acac), 4, 4 Phosphorescent host material such as'-bis (9H-carbazole-9-yl) biphenyl (CBP), 3,3'-di (9H-carbazole-9-yl) -1,1'-biphenyl (mCBP), ADN , Fluorescent host materials such as Alq3, and polymer materials such as polyphenylene vinylene (PPV) and MEH-PPV, but are not limited thereto.
  • DCM 2 -2-methyl-6-juloridyl-9-enyl-4H-pyran
  • Phosphorescent host material such as'-bis (9H-carbazole-9-yl) biphenyl (CBP), 3,3'-di (9H-carbazole-9-yl
  • the material for forming the light emitting layer may be used alone or in combination of two or more.
  • the material for forming the light emitting layer is appropriately selected according to the desired emission wavelength.
  • the organic semiconductor that is the material for forming the film 10 preferably has a molecular weight of 300 to 1000.
  • the molecular weight of the organic semiconductor is more preferably 400 or more. Further, the molecular weight of the organic semiconductor is more preferably 900 or less.
  • the molecular weight of the organic semiconductor is 300 or more, the glass transition point (Tg) of the organic semiconductor becomes high, and the heat resistance of the organic semiconductor film is improved.
  • the molecular weight is 1000 or less, the vapor pressure of the organic semiconductor becomes high, and the vapor deposition can be performed at the thermal decomposition temperature or less.
  • the upper limit value and the lower limit value of the molecular weight of the organic semiconductor can be arbitrarily combined.
  • the molecular weight of the organic semiconductor may be 300 to 900, 400 to 1000, or 400 to 900.
  • the molecular weight of the organic semiconductor can be determined by measurement using TOF-SIMS (Time-of-Flight Second Method Ion Mass Spectrometry).
  • the film 10 may further contain a dopant.
  • a dopant a known one can be used, and an appropriate material can be selected according to the function of the apparatus provided with the film 10 of the present embodiment. By including the dopant, the film 10 can be made more conductive.
  • NDP-2 Novaled Co.
  • examples of the dopant used as the electron injection material include 8-hydroxyquinolinolato-lithium (Liq), NDN-1 (manufactured by Novaled), NDN-26 (manufactured by Novaled) and the like.
  • FIG. 3 to 5 are schematic views showing a process of manufacturing the above-mentioned film 10.
  • a substrate 50 on which the film 10 is formed is prepared.
  • Such a substrate 50 is installed in the chamber 500 of the vacuum vapor deposition apparatus, and the organic semiconductor 51a and the fluorine-containing polymer 52a are provided from the organic semiconductor vapor deposition source (rutsubo) 51 and the fluorine-containing polymer vapor deposition source (rutsubo) 52. Is supplied and co-deposited.
  • FIG. 3 shows that the organic semiconductor and the fluorine-containing polymer are vapor-deposited from different vapor deposition sources, they may be vapor-deposited from the same vapor deposition source.
  • the organic semiconductor 51a and the fluorine-containing polymer 52a the organic semiconductor and the fluorine-containing polymer constituting the above-mentioned film 10 can be used, respectively.
  • the vapor deposition conditions are set so that the ratio of the fluorine-containing polymer to the total of the fluorine-containing polymer and the organic semiconductor is 20 to 80% by volume in the co-deposited film formed on the substrate 50.
  • the organic semiconductor 51a is preferably one that does not decompose by heating during vapor deposition.
  • the fact that the organic semiconductor is not decomposed by heating during vapor deposition can be determined by determining the weight reduction rate of the organic semiconductor to be used by the following method.
  • thermogravimetric differential thermal analyzer manufactured by Hitachi High-Tech Science Co., Ltd .: STA7200
  • the weight loss rate at normal pressure at T d50 is 1% or less, it is determined that the reason for the weight loss at T d50 under reduced pressure is not thermal decomposition but sublimation. It can be determined that such an organic semiconductor does not decompose by heating during vapor deposition, that is, it is a material suitable for vapor deposition. On the other hand, when the weight loss rate at normal pressure at T d50 exceeds 1%, it is determined that the reason for the weight loss at T d50 under reduced pressure is thermal decomposition. Since such an organic semiconductor is decomposed by heating during vapor deposition, it can be judged that it is not suitable for vapor deposition.
  • the organic semiconductor and the fluorine-containing polymer are co-deposited, the organic semiconductor and the fluorine-containing polymer are phase-separated on the substrate, and the domain 51b of the organic semiconductor and the domain of the fluorine-containing polymer are separated. It is considered that 52b and 52b are formed. It is considered that the size (diameter) of the domain 52b of the fluorine-containing polymer falls within a certain numerical range with a small variation depending on the relationship between the surface energy of the substrate 50 to be co-deposited and the surface energy of the fluorine-containing polymer. Be done.
  • the domain 52b is considered to be large and easily spread, and when the fluorine-containing polymer is difficult to spread on the surface of the substrate 50, the domain 52b is spread. It is thought that the diameter tends to be small.
  • the organic semiconductor 51a sublimated from the vapor deposition source 51 is energetically more stable than the deposition in the domain 52b, so that it is considered that the organic semiconductor 51a is deposited in the domain 51b of the organic semiconductor.
  • the fluorine-containing polymer 52a sublimated from the vapor deposition source 52 is more energetically stable than depositing in the domain 51b, it is considered that the fluorine-containing polymer 52a is deposited in the domain 52b of the fluorine-containing polymer.
  • the domain 51b of the organic semiconductor continuous in the film thickness direction of the co-deposited film and the domain 52b of the fluorine-containing polymer continuous in the film thickness direction of the co-deposited film are formed.
  • the diameter of the domain 52b does not change significantly in the film thickness direction of the co-deposited film, and is the size of the first domain 52b formed on the surface of the substrate 50. It will reflect the above.
  • the fluorine-containing polymer constituting the domain 52b has a narrow molecular weight, and the difference in physical properties between the initial stage and the final stage of vapor deposition becomes small. Therefore, the quality of the obtained film 10 is likely to be stable.
  • the film 10 is manufactured as described above.
  • the domains 52b are easily moved by the heating, and the adjacent domains 52b may coalesce and the nanodomain structure of the film 10 may be destroyed.
  • the fluorine-containing polymer used satisfies the above-mentioned requirements (4) and (5), the domain 52b is difficult to unite, and the film 10 easily maintains the nanodomain structure.
  • the fluorine-containing polymer having the above-mentioned structure it is possible to provide a fluorine-containing polymer having high heat resistance and suitable for vapor deposition. Further, according to the film having the above-mentioned structure, the film has a low refractive index, high transparency, high heat resistance, and stable quality. Further, according to the method for producing a film having the above-mentioned structure, such a film can be easily produced.
  • the fluorine-containing polymer of the present embodiment and the organic semiconductor are co-deposited to form the film 10, but the present invention is not limited to this.
  • the film containing the fluorine-containing polymer and the organic semiconductor of the present embodiment may be produced by a wet process such as coating.
  • FIG. 6 is a schematic cross-sectional view showing an organic photoelectronic device (organic EL device) 100 according to a second embodiment of the present invention.
  • the organic EL element 100 has a structure in which a substrate 110, an anode 111, a hole injection layer 112, a hole transport layer 113, a light emitting layer 114, an electron transport layer 115, an electron injection layer 116, and a cathode 117 are laminated in this order. There is.
  • the organic EL element 100 of the present embodiment employs a top emission method in which the light L generated in the light emitting layer 114 is emitted to the outside via the cathode 117.
  • the substrate 110 may or may not have light transmission.
  • an inorganic substance such as glass, quartz glass, or silicon nitride, or an organic polymer (resin) such as a polyimide resin, an acrylic resin, or a polycarbonate resin can be used.
  • an organic polymer such as a polyimide resin, an acrylic resin, or a polycarbonate resin
  • a metal material can be adopted as a material for forming the substrate 110.
  • the substrate 110 includes various wirings and driving elements (not shown) that are electrically connected to the organic EL element.
  • the anode 111 is formed on the substrate 110 and supplies holes to the hole transport layer 113. Further, the anode 111 has a light reflectivity that reflects the light emitted from the light emitting layer 114.
  • a conductive metal oxide such as ITO (Indium Tin Oxide: indium-doped tin oxide) or IZO (Indium Zinc Oxide: indium-doped zinc oxide) can be used.
  • a reflective film made of a metal material is provided on the substrate 110 side of the anode 111. That is, the anode 111 has a laminated structure of a layer made of a conductive metal oxide as a forming material and a reflective film. Further, silver may be used as a material for forming the anode 111.
  • the thickness of the anode 111 is not particularly limited, but is preferably 30 to 300 nm.
  • the thickness of the anode 111 is, for example, 100 nm.
  • the hole injection layer 112 is formed between the anode 111 and the hole transport layer 113.
  • the hole injection layer 112 has a function of facilitating the injection of holes from the anode 111 into the hole transport layer 113.
  • the hole injection layer 112 does not have to be formed.
  • the hole injection layer 112 can be formed by using the hole injection material described above.
  • the thickness of the hole injection layer 112 is not particularly limited, but is preferably 1 to 100 nm.
  • the thickness of the hole injection layer 112 is, for example, 5 nm.
  • the hole transport layer 113 is formed on the hole injection layer 112.
  • the hole transport layer 113 has a function of satisfactorily transporting the holes injected from the anode 111 toward the light emitting layer 114.
  • the hole transport layer 113 can be formed by using the hole transport material described above.
  • the hole transport layer 113 may be a single layer, or may have a configuration in which a plurality of layers of hole transport materials are laminated.
  • the hole transport materials constituting each layer may be the same or different from each other.
  • Hole transport layer 113 is preferably an absorption coefficient in the wavelength range 450 ⁇ 800 nm is 5000 cm -1 or less, more preferably 1000 cm -1 or less, to have no absorption band in the wavelength region in particular preferable.
  • the absorption coefficient of each layer constituting the hole transport layer 113 exceeds 5000 cm-1 , once the light passes through the hole transport layer having a thickness of 100 nm, it is 5% compared to the case where the total amount of light before passing is 100%. Light is absorbed. Inside the organic EL element, the loss due to the absorption of light when passing through the hole transport layer 113 is accumulated due to the multiple interference of light. Therefore, light absorption when passing through the hole transport layer becomes a factor that greatly reduces the light extraction efficiency.
  • the thickness of the hole transport layer 113 is not particularly limited, but is preferably 10 to 250 nm, more preferably 20 to 150 nm.
  • the light emitting layer 114 is formed on the hole transport layer 113. In the light emitting layer 114, the holes injected from the anode 111 and the electrons injected from the cathode 117 are recombined to emit photons to emit light. The emission wavelength at that time is determined according to the material for forming the light emitting layer 114.
  • the light emitting layer 114 corresponds to the "active layer" in the present invention.
  • the light emitting layer 114 can be formed by using the above-mentioned material for forming the light emitting layer.
  • the material for forming the light emitting layer may be used alone or in combination of two or more, and is appropriately selected according to a desired emission wavelength.
  • the thickness of the light emitting layer 114 is not particularly limited, but is preferably 10 to 30 nm.
  • the thickness of the light emitting layer 114 is, for example, 15 nm.
  • the electron transport layer 115 is formed on the light emitting layer 114.
  • the electron transport layer 115 has a function of satisfactorily transporting the electrons injected from the cathode 117 toward the light emitting layer 114.
  • the electron transport layer 115 can be formed by using the electron transport material described above.
  • the thickness of the electron transport layer 115 is not particularly limited, but is preferably 30 to 80 nm.
  • the thickness of the electron transport layer 115 is, for example, 60 nm.
  • the electron injection layer 116 is provided between the cathode 117 and the electron transport layer 115.
  • the electron injection layer 116 has a function of facilitating the injection of electrons from the cathode 117 into the electron transport layer 115.
  • the above-mentioned electron injection material can be used as the material for forming the electron injection layer 116.
  • the electron injection layer 116 does not have to be formed.
  • the thickness of the electron injection layer 116 is not particularly limited, but is preferably 0.5 to 2 nm.
  • the thickness of the electron injection layer 116 is, for example, 1 nm.
  • the cathode 117 is formed on the electron injection layer 116.
  • the cathode 117 has a function of injecting electrons into the electron injection layer 116.
  • a material for forming the cathode 117 a known material can be adopted.
  • examples of the material for forming the cathode 117 include an MgAg electrode and an Al electrode.
  • a buffer layer such as LiF may be formed on the surface of the cathode 117.
  • the cathode 117 is a semi-transmissive film formed thin enough to reflect a part of the light emitted from the light emitting layer 114 as a whole and pass through the rest.
  • the thickness of the cathode 117 is not particularly limited, but is preferably 5 to 30 nm.
  • the thickness of the cathode 117 is, for example, 5 nm.
  • the anode 111 and the cathode 117 form an optical resonance structure (microcavity) in which light is resonated between the anode 111 and the cathode 117.
  • the light generated by the light emitting layer 114 is repeatedly reflected between the anode 111 and the cathode 117, and the light having a wavelength matching the optical path length between the anode 111 and the cathode 117 is resonated and amplified.
  • light having a wavelength that does not match the optical path length between the anode 111 and the cathode 117 is attenuated.
  • the "optical path length" referred to here is calculated using the wavelength of the desired light emitted to the outside of the device and the refractive index of each layer at the desired wavelength of the light.
  • the optical path length between the anode 111 and the cathode 117 is set to, for example, an integral multiple of the center wavelength of the light L generated in the light emitting layer 114.
  • the light L emitted by the light emitting layer 114 is amplified as it is closer to the center wavelength, attenuated as it is farther from the center wavelength, and is emitted to the outside of the organic EL element 100.
  • the light L emitted from the organic EL element 100 has a narrow half-value width of the emission spectrum and improved color purity.
  • the microcavity structure utilizes resonance due to fixed-end reflection with the cathode and anode at both ends. Therefore, "the optical path length from the light emitting position to the anode is an integral multiple of 1/4 of the wavelength ⁇ of the desired light emitted to the outside of the element", and “the optical path length from the light emitting position to the cathode is outside the element”. If it is "an integral multiple of 1/4 of the wavelength ⁇ of the desired light emitted into the light", the desired microcavity structure can be formed.
  • the organic EL device 100 of the present embodiment contains the above-mentioned fluorine-containing polymer in any one or more layers described above.
  • the organic EL device 100 of the present embodiment preferably contains the above-mentioned fluorine-containing polymer in at least one of the hole injection layer 112 and the hole transport layer 113.
  • the hole transport layer 113 is a laminate of layers of hole transport materials, at least one of the layers contains the above-mentioned fluorine-containing polymer.
  • the organic EL element 100 of the present embodiment preferably contains the above-mentioned fluorine-containing polymer in at least one of the electron transport layer 115 and the electron injection layer 116.
  • the electron transport layer 115 is a laminate of layers of electron transport materials
  • at least one of the layers contains the above-mentioned fluorine-containing polymer.
  • the organic EL device 100 of the present embodiment contains the above-mentioned fluorine-containing polymer in at least one of the hole injection layer 112 and the hole transport layer 113, and at least one of the electron transport layer 115 and the electron injection layer 116. Is preferable.
  • each layer containing the above-mentioned fluorine-containing polymer has a lower refractive index than the case where these layers do not contain the above-mentioned fluorine-containing polymer. Therefore, the organic EL element 100 of the present embodiment improves the light extraction efficiency and the external quantum efficiency. As a result, the organic EL element 100 of the present embodiment can obtain the same amount of light emission as the conventional organic EL element with a smaller input power as compared with the conventional organic EL element that does not contain the above-mentioned fluorine-containing polymer. In addition, each layer containing the above-mentioned fluorine-containing polymer has high heat resistance. Therefore, the organic EL element 100 of the present embodiment is a highly reliable organic EL element 100.
  • the heat resistance of the organic EL element 100 can be evaluated by the following method.
  • ⁇ Heat resistance evaluation 1> Manufacturing of element 1 for conducting conductivity evaluation
  • a glass substrate on which ITO (indium tin oxide) is formed in a 2 mm wide strip is used.
  • the substrate is ultrasonically cleaned with a neutral detergent, acetone, and isopropanol, and then boiled and washed in isopropanol, and then the deposits on the surface of the ITO film are removed by ozone treatment.
  • the washed substrate is placed in a vacuum vapor deposition machine, the pressure is reduced to 10 -4 Pa or less, and molybdenum trioxide is vapor-deposited on the substrate.
  • the vapor deposition rate is 0.1 nm / sec, and a 5 nm film is formed to prepare a hole injection layer.
  • ⁇ -NPD and a fluorine-containing polymer are co-deposited on the hole injection layer.
  • the total vapor deposition rate of the two materials is 0.2 nm / sec, and a 100 nm film is formed to prepare a charge transport layer.
  • the vapor deposition rate is adjusted so that the volume ratio of ⁇ -NPD to the fluorine-containing polymer in the charge transport layer is a desired ratio.
  • the N 2 atmosphere heating 60 minutes element 1 at 80 ° C. on a hot plate. After returning the element 1 to room temperature, the current flowing through the element is measured again to obtain the current density (J) (unit: mA / cm 2) with respect to the electric field (E) (unit: MV / cm). Then, the N 2 atmosphere, the same element 1 is heated 60 minutes at 90 ° C. on a hot plate. After returning the element 1 to room temperature, the current flowing through the element is measured again to obtain the current density (J) (unit: mA / cm 2) with respect to the electric field (E) (unit: MV / cm).
  • the heat resistance of the element 1 is evaluated as follows. ⁇ : After heating to 80 ° C, the current density of 0.4 MV / cm is less than 90% of the initial value ⁇ : After heating to 90 ° C, the current density of 0.4 MV / cm is less than 90% of the initial value ⁇ : Heating to 90 ° C. After that, the current density of 0.4 MV / cm is 90% or more of the initial value.
  • HAT-CN was used instead of molybdenum trioxide
  • HT211 was used instead of ⁇ -NPD. ..
  • the current density of 0.4 MV / cm is less than 90% of the initial value ⁇ ⁇ : After heating to 130 ° C, the current density of 0.4 MV / cm is less than 90% of the initial value ⁇ ⁇ ⁇ : After heating to 130 ° C, 0 .4 MV / cm current density is 90% or more of the initial value
  • the above-mentioned fluorine-containing polymer may be introduced into each layer as a co-deposited film co-deposited with the organic semiconductors constituting each layer at the time of production.
  • the hole injection layer 112 and the hole transport layer 113 both contain the above-mentioned fluorine-containing polymer
  • the hole injection material and the fluorine-containing polymer are co-deposited to form a co-deposit film.
  • the hole transport material and the fluorine-containing polymer may be co-deposited to form the co-deposited film (second film).
  • the organic EL device 100 having the above configuration, since at least one of the hole injection layer 112 and the hole transport layer 113 contains the above-mentioned fluorine-containing polymer, the external quantum efficiency is improved and the power consumption is increased. There are few organic EL elements.
  • FIG. 7 is an explanatory diagram of the organic EL element 200 according to the third embodiment of the present invention, and is a diagram corresponding to FIG.
  • the organic EL element 200 has a structure in which a substrate 210, an anode 211, a hole injection layer 112, a hole transport layer 113, a light emitting layer 114, an electron transport layer 115, an electron injection layer 116, and a cathode 217 are laminated in this order. There is.
  • the organic EL element 200 of the present embodiment employs a bottom emission method in which the light L generated in the light emitting layer 114 is emitted to the outside via the anode 211 and the substrate 210.
  • the substrate 210 has light transmission.
  • an inorganic substance such as glass, quartz glass, or silicon nitride, or an organic polymer (resin) such as a polyimide resin, an acrylic resin, or a polycarbonate resin can be used. Further, if it has light transmission property, a composite material formed by laminating or mixing the above materials can also be used.
  • the anode 211 is formed on the substrate 210 and supplies holes to the hole transport layer 113.
  • a conductive metal oxide having light transmittance such as ITO and IZO can be used.
  • the cathode 217 is formed on the electron injection layer 116.
  • the cathode 217 has a function of injecting electrons into the electron injecting layer 116. Further, the cathode 217 has a function of reflecting the light L emitted isotropically in the light emitting layer 114 and directing the light L toward the anode 211.
  • a material for forming the cathode 217 MgAg, Ag, Al and the like can be used.
  • a buffer layer such as LiF may be formed on the surface of the cathode 217.
  • the thickness of the cathode 217 is not particularly limited, but is preferably 30 to 300 nm. The thickness of the cathode 217 is, for example, 100 nm.
  • the organic EL element 200 having such a configuration preferably contains the above-mentioned fluorine-containing polymer in any one or more layers described above. Specifically, the organic EL element 200 preferably contains the above-mentioned fluorine-containing polymer in at least one layer of the hole injection layer 112 and the hole transport layer 113. Further, the organic EL element 200 preferably contains the above-mentioned fluorine-containing polymer in at least one layer of the electron transport layer 115 and the electron injection layer 116.
  • the organic EL element 200 preferably contains the above-mentioned fluorine-containing polymer in at least one of the hole injection layer 112 and the hole transport layer 113, and at least one of the electron transport layer 115 and the electron injection layer 116.
  • the organic EL element 200 has improved light extraction efficiency as compared with the conventional organic EL element that does not contain a fluorine-containing polymer.
  • the organic EL element 200 of the present embodiment is a highly reliable organic EL element 200.
  • the heat resistance of the organic EL element 200 can be evaluated by the same method as the heat resistance of the organic EL element 100 described above.
  • the organic EL element 100 or the organic EL element 200 may have other functional layers arranged between the layers. For example, a hole block layer or an electron block layer may be arranged between the light emitting layer and the charge transport layer, or an adjusting layer for forming the above-mentioned microcavity structure may be arranged.
  • a wavelength conversion layer containing quantum dots may be arranged in the light emission direction. By having such a wavelength conversion layer, it becomes an organic EL element in which the color purity of the emitted light is improved.
  • quantum dots may be used as a material for forming the light emitting layer 114.
  • colloidal quantum dots that can be dispersed in a solution can also be used.
  • colloidal quantum dots can be formed by using a general wet coating technique.
  • the type of quantum dots is not particularly limited, and perovskite quantum dots, carbon-based quantum dots, alloy-type quantum dots, core-shell type quantum dots, and core-type quantum dots can be used.
  • the organic EL device has been described as an example of the organic photoelectronic device, but the organic photoelectronic device to which the film containing the fluorine-containing polymer of the present invention is applied is not limited to the organic EL device.
  • the organic photoelectronic device of the present invention may be, for example, an organic semiconductor laser. A known configuration can be adopted as the organic semiconductor laser. By adopting a film containing the above-mentioned fluorine-containing polymer as one of the films made of organic semiconductors constituting the organic semiconductor laser, the organic semiconductor laser having improved external quantum efficiency can be obtained.
  • the organic photoelectron element of the present invention may be, for example, a light receiving element such as an optical sensor or a solar cell.
  • optical sensor and the solar cell can be adopted for the optical sensor and the solar cell.
  • An optical sensor with improved detection performance and a solar cell with improved power generation efficiency by adopting a film containing the above-mentioned fluorine-containing polymer as one of the films composed of an optical sensor and an organic semiconductor constituting a solar cell. It becomes.
  • thermogravimetric reduction rate of fluorine-containing polymer under vacuum The measurement was performed using a vacuum differential thermal balance (manufactured by Advance Riko Co., Ltd .: VPE-9000). Were charged fluoropolymer 50mg to the cells of the inner diameter 7 mm, at 1 ⁇ 10 -3 Pa vacuum degree, when the temperature was raised per minute 2 °C to 500 ° C. from room temperature, the initial weight of the fluoropolymer ( The weight loss rate (%) with respect to 50 mg) was measured. The temperature at which the weight loss rate was 100% (T d100 ), the temperature at which the weight loss rate was 10% (T d10 ), and the temperature at which the weight loss rate was 90% (T d90 ) were determined.
  • the storage elastic modulus adopts a value measured using a dynamic viscoelasticity measuring device (manufactured by Anton Pearl Co., Ltd., MCR502) and a heating furnace for a viscoelasticity measuring device (manufactured by Anton Pearl Co., Ltd., CTD450). .. Specifically, the sample (fluorine-containing polymer) was heated to a temperature equal to or higher than the melting point, and then cooled at 2 ° C./min in a constant-speed temperature lowering mode.
  • the storage elastic modulus (G') was measured under the conditions of a strain of 0.01% and a frequency of 1 Hz, and the temperature at which G'and G'at 25 ° C. became less than 1 ⁇ 10 6 Pa was determined.
  • the temperature of the polymerization tank was maintained at 60 ° C., and 18.9 mL of a 0.53 mass% solution (solvent: AE-3000) of t-butylperoxypivalate (PBPV) was charged to initiate polymerization. Since the polymerization pressure decreases as the polymerization progresses during the polymerization, TFE was continuously introduced into the polymerization tank so that the polymerization pressure became substantially constant.
  • the polymerization pressure was maintained at 1.04 ⁇ 0.04 MPaG (gauge pressure).
  • the "gauge pressure” is a relative pressure with an atmospheric pressure of 0 MPaG, and refers to a difference from an absolute pressure with a vacuum of zero.
  • TFE unit 2:98 (mol%).
  • the obtained polymer was heated in an oven at 330 ° C., immersed in methanol, and heated in an oven at 75 ° C. for 40 hours to replace the terminal group with a methyl ester group to obtain the fluorine-containing polymer A. Obtained.
  • the obtained fluorine-containing polymer A 44 g was charged into the raw material charging section of the above-mentioned glass tube type sublimation purification apparatus, and the pressure inside the collecting section was reduced to 3.0 ⁇ 10 -3 Pa.
  • the raw material charging portion was gradually heated to 330 ° C. to sublimate the fluorine-containing polymer A.
  • the collecting portion was heated at set temperatures of 310 ° C., 280 ° C., and 250 ° C. from the side closer to the charging portion. Of these, the substance precipitated in the collection section at the set temperature of 280 ° C. was recovered to obtain 4 g of the purified fluorine-containing polymer A1.
  • the fluorinated polymer B was sublimated in the same manner as in Synthesis Example 1 except that 20 g of the fluorinated polymer B was used. The substance precipitated in the collection section at a set temperature of 250 ° C. was recovered to obtain 2 g of purified fluorine-containing polymer B1.
  • the terminal group of the fluorine-containing polymer was replaced with a methyl ester group in the same manner as in Synthesis Example 1 to obtain a fluorine-containing polymer D.
  • the fluorine-containing polymer D was sublimated in the same manner as in Synthesis Example 1.
  • the substance precipitated in the collection section at the set temperature of 250 ° C. and 280 ° C. was recovered to obtain 5 g of the purified fluorine-containing polymer D1.
  • the terminal group of the fluorine-containing polymer was replaced with 3 -CF groups under the same conditions as in Synthesis Example 3 to obtain a fluorine-containing polymer E.
  • the fluorine-containing polymer E was sublimated in the same manner as in Synthesis Example 2 to obtain 4 g of the purified fluorine-containing polymer E1.
  • the terminal group of the fluorine-containing polymer was replaced with a methyl ester group in the same manner as in Synthesis Example 1 to obtain a fluorine-containing polymer F.
  • the fluorine-containing polymer F was sublimated in the same manner as in Synthesis Example 1 to obtain 4 g of the purified fluorine-containing polymer F1.
  • the terminal group of the fluorine-containing polymer was replaced with 3 -CF groups under the same conditions as in Synthesis Example 3 to obtain a fluorine-containing polymer G.
  • the fluorine-containing polymer G was sublimated in the same manner as in Synthesis Example 3.
  • the substance precipitated in the collection section at the set temperature of 250 ° C., 280 ° C. and 310 ° C. was recovered to obtain 6 g of the purified fluorine-containing polymer G1.
  • the obtained fluorine-containing polymer was heated in an oven at 330 ° C., then immersed in methanol and heated in an oven at 75 ° C. for 40 hours to replace the terminal group with a methyl ester group, and the fluorine-containing polymer was used.
  • the fluorine-containing polymer H was sublimated in the same manner as in Synthesis Example 1 to obtain 4 g of the purified fluorine-containing polymer H1.
  • the obtained polymer was heated in an oven at 300 ° C., then immersed in methanol and heated in an oven at 75 ° C. for 20 hours to replace the terminal group with a methyl ester group to obtain the fluorine-containing polymer I. Obtained.
  • the fluorine-containing polymer I was sublimated and purified in the same manner as in Synthesis Example 4 to obtain 4 g of the purified fluorine-containing polymer I1.
  • TFE Since the pressure in the polymerization tank decreases as the polymerization progresses, TFE was continuously charged so that the polymerization pressure became almost constant. The polymerization pressure was maintained at 1.34 MPaG. A 1.5% by mass solution (solvent: R113) of bis (perfluorobutyryl) peroxide was intermittently charged in the polymerization tank, and the polymerization was terminated when 86 g of TFE was consumed to obtain a fluorine-containing copolymer J. .. The amount of TFE consumed was determined from the amount of mass loss of the TFE gas cylinder.
  • the fluorine-containing polymer J was sublimated in the same manner as in Synthesis Example 4 to obtain 4 g of the purified fluorine-containing polymer J1.
  • Fluoron PFA AGC's Fluoron PFA P-63
  • the physical properties of the synthesized fluorine-containing polymer were measured by the above-mentioned method. The measured physical properties are shown in Table 1.
  • the fluorine-containing resins A1 to G1 and J1 satisfy the requirements (1) to (3) shown in the above-described embodiment, while the fluorine-containing polymers B, H and FluonPFA satisfy the requirement (2). ), (3), it can be seen that the fluorine-containing polymers I1, H1 and H do not satisfy the requirement (1). Since the fluorine-containing polymer I1 is amorphous and has no crystallinity, its melting point was not detected.
  • Evaluations 1 to 5 were carried out below using the fluorine-containing polymers shown in Table 1.
  • Increase ratio of chamber pressure during vapor deposition Maximum pressure during vapor deposition / Initial pressure before vapor deposition Fluorine-containing polymers whose chamber pressure increase ratio is 2 times or less are evaluated as “good products” and the increase ratio exceeds 2 times. The fluorine-containing polymer was evaluated as "defective”.
  • ⁇ Evaluation 2 Refractive index> [Preparation of sample for refractive index measurement] An organic semiconductor ⁇ -NPD and a fluorine-containing polymer were co-deposited on a silicon substrate to form a 100 nm co-deposited film to obtain a sample for refractive index measurement. The total deposition rate of the two materials was 0.2 nm / sec. The vapor deposition rate was adjusted so that the volume ratio of ⁇ -NPD to the fluorine-containing polymer in the co-deposited film was set to a desired ratio.
  • ⁇ Evaluation 3 Haze> [Preparation of sample for haze measurement] ⁇ -NPD and a fluorine-containing polymer were co-deposited on a glass substrate to form a 100 nm co-deposited film to obtain a sample for haze measurement. The total deposition rate of the two materials was 0.2 nm / sec. The vapor deposition rate was adjusted so that the volume ratio of ⁇ -NPD to the fluorine-containing polymer in the co-deposited film was set to a desired ratio.
  • the haze measurement was performed using a haze meter (Haze Guard K50-290, manufactured by Toyo Seiki Co., Ltd.). After measuring the initial haze of the haze measurement sample, the sample was heated on a hot plate heated to 100 ° C. for 1 hour. After returning the sample to room temperature, the haze was measured again. Further, the sample was heated on a hot plate heated to 120 ° C. for 1 hour, and the haze was measured in the same manner.
  • a haze meter Haze Guard K50-290, manufactured by Toyo Seiki Co., Ltd.
  • the obtained haze was evaluated as follows. ⁇ : Less than 0.2 ⁇ : 0.2 or more and less than 0.5 ⁇ : 0.5 or more
  • ⁇ Evaluation 4 Heat resistance 1> [Manufacturing of element 1 for conducting conductivity evaluation] A glass substrate on which ITO (indium tin oxide) was formed into a strip having a width of 2 mm was used. The substrate was ultrasonically cleaned with a neutral detergent, acetone, and isopropanol, and then boiled and washed in isopropanol, and then the deposits on the surface of the ITO film were removed by ozone treatment. The washed substrate was placed in a vacuum vapor deposition machine, the pressure was reduced to 10 -4 Pa or less, and molybdenum trioxide was vapor-deposited on the substrate. The vapor deposition rate was 0.1 nm / sec, and a 5 nm film was formed to prepare a hole injection layer.
  • ITO indium tin oxide
  • ⁇ -NPD and a fluorine-containing polymer were co-deposited on the hole injection layer.
  • the total vapor deposition rate of the two materials was 0.2 nm / sec, and a 100 nm film was formed to prepare a charge transport layer.
  • the vapor deposition rate was adjusted so that the volume ratio of ⁇ -NPD to the fluorine-containing polymer in the charge transport layer was set to a desired ratio.
  • aluminum was deposited on the charge transport layer in the form of a strip having a width of 2 mm.
  • the strip-shaped aluminum film was orthogonal to the ITO film in the field of view seen from the vertical direction of the substrate.
  • the heat resistance of the element 1 was evaluated as follows. ⁇ : After heating to 80 ° C, the current density of 0.4 MV / cm is less than 90% of the initial value ⁇ : After heating to 90 ° C, the current density of 0.4 MV / cm is less than 90% of the initial value ⁇ : Heating to 90 ° C. After that, the current density of 0.4 MV / cm is 90% or more of the initial value.
  • the heating temperature was set to 100 ° C., 110 ° C., 120 ° C., and 130 ° C., and the heating time was set to 15 minutes, respectively.
  • the current density (J) (unit: mA / cm 2 ) was determined.
  • the heat resistance of the element 2 was evaluated as follows. ⁇ : After heating to 100 ° C, the current density of 0.4 MV / cm is less than 90% of the initial value ⁇ : After heating to 110 ° C, the current density of 0.4 MV / cm is less than 90% of the initial value ⁇ : Heating to 120 ° C. After, the current density of 0.4 MV / cm is less than 90% of the initial value ⁇ ⁇ : After heating to 130 ° C, the current density of 0.4 MV / cm is less than 90% of the initial value ⁇ ⁇ ⁇ : After heating to 130 ° C, 0 .4 MV / cm current density is 90% or more of the initial value
  • Evaluations 1 to 3 and 5 described above were carried out using the fluorine-containing polymer A1.
  • the vapor deposition rate was adjusted in the co-evaporation of the organic semiconductor and the fluorine-containing polymer, and the volume ratio of the organic semiconductor and the fluorine-containing polymer was set to 50:50.
  • Example 2 In the sample preparation, the evaluation was carried out in the same manner as in Example 1 except that the vapor deposition rate was adjusted and the volume ratio of the organic semiconductor to the fluorine-containing polymer was 80:20.
  • Example 3 The evaluation was carried out in the same manner as in Example 1 except that the vapor deposition rate was adjusted in the sample preparation and the volume ratio of the organic semiconductor to the fluorine-containing polymer was set to 20:80.
  • Evaluations 1 to 5 described above were carried out using the fluorine-containing polymer B1.
  • the vapor deposition rate was adjusted in the co-evaporation of the organic semiconductor and the fluorine-containing polymer, and the volume ratio of the organic semiconductor and the fluorine-containing polymer was set to 50:50.
  • Example 5 The evaluation was carried out in the same manner as in Example 1 except that B2 was used as the fluorine-containing polymer.
  • Example 6 The evaluation was carried out in the same manner as in Example 1 except that C1 was used as the fluorine-containing polymer.
  • Example 7 The evaluation was carried out in the same manner as in Example 4 except that D1 was used as the fluorine-containing polymer.
  • Example 8 The evaluation was carried out in the same manner as in Example 1 except that E1 was used as the fluorine-containing polymer.
  • Example 9 The evaluation was carried out in the same manner as in Example 1 except that F1 was used as the fluorine-containing polymer.
  • Example 10 The evaluation was carried out in the same manner as in Example 1 except that G1 was used as the fluorine-containing polymer.
  • Example 11 The evaluation was carried out in the same manner as in Example 1 except that J1 was used as the fluorine-containing polymer.
  • Example 12 The evaluation was carried out in the same manner as in Example 4 except that H1 was used as the fluorine-containing polymer.
  • Example 13 The evaluation was carried out in the same manner as in Example 1 except that B was used as the fluorine-containing polymer.
  • Example 14 The evaluation was carried out in the same manner as in Example 1 except that H was used as the fluorine-containing polymer.
  • Evaluations 1 to 4 were performed using the fluorine-containing polymer I1.
  • the vapor deposition rate was adjusted in the co-evaporation of the organic semiconductor and the fluorine-containing polymer, and the volume ratio of the organic semiconductor and the fluorine-containing polymer was set to 50:50.
  • Example 16 Using a commercially available fluorine-containing polymer, Fluon PTFE, evaluation 1: change in chamber pressure during vapor deposition was evaluated. In Evaluation 1, the rise in the chamber during vapor deposition was extremely large, so no other evaluation requiring co-deposition was performed.
  • Example 17 As an example in which the fluorine-containing polymer was not used, evaluations 2 to 4 described above were carried out using a sample in which a single film of ⁇ -NPD was formed at a vapor deposition rate of 0.1 nm / sec.
  • Example 18 As an example in which the fluorine-containing polymer was not used, evaluation 5 was performed using a sample in which a single film of HT211 was formed at a vapor deposition rate of 0.1 nm / sec.
  • Examples 1 to 18 correspond to Examples, and Examples 12 to 18 correspond to Comparative Examples. The results are shown in Table 2.
  • Example 1 As a result of the evaluation, it was found that in Examples 1 to 11, stable vapor deposition was possible without an increase in the chamber internal pressure during vapor deposition. Further, in Examples 1 to 11, it was found that the increase in haze was suppressed even when heated. Further, it was found that the elements 1 and 2 of Examples 1 to 11 are excellent in heat resistance. On the other hand, in Examples 13, 14 and 16, it was found that an increase in the chamber internal pressure during vapor deposition was observed, and the vapor deposition state may become unstable. Further, in Examples 12, 14, 15 and 17, it was found that the haze was increased by heating. In Example 17, it is considered that ⁇ -NPD was melted by heating and then crystallization proceeded to generate a scattering source.
  • Examples 12, 14 and 15 it is considered that the nanodomain structure of the co-deposited film was changed by heating and a scattering source was generated inside the co-deposited film. Further, in Examples 12, 14 and 15, it was found that the heat resistance of the elements 1 and 2 was low. From the above results, it was confirmed that the present invention is useful.
  • the entire contents of the specification, claims, abstract and drawings of Japanese Patent Application No. 2020-030460 filed on February 26, 2020 are cited here as disclosure of the specification of the present invention. It is something to incorporate.

Abstract

Provided is a fluorine-containing polymer that is suitable for vapor deposition. Also provided is a film that contains such a fluorine-containing polymer as a material. Also provided is a film manufacturing method with which such a film can be easily manufactured. Also provided is an organic opto-electronic element having such a film in the structure thereof.　The fluorine-containing polymer satisfies (1)-(3). (1) The melting point is at least 200°C. (2) The thermogravimetric reduction rate when the temperature is increased at a heating rate of 2°C/min at a pressure of 1×10-3Pa reaches essentially 100% at a temperature of at most 400°C. (3) The temperature range from the temperature at which the thermogravimetric reduction rate is 10% to the temperature at which the thermogravimetric reduction rate is 90% when the temperature is increased at a heating rate of 2°C/min at a pressure of 1×10-3Pa is within 100°C.

Description

含フッ素重合体、膜、膜の製造方法および有機光電子素子Fluorine-containing polymer, film, film manufacturing method and organic photoelectron device
　本発明は、含フッ素重合体、膜、膜の製造方法および有機光電子素子に関する。 The present invention relates to a fluorine-containing polymer, a film, a method for producing a film, and an organic photoelectron device.
　従来、自発光型の素子として、有機光電子素子（有機エレクトロルミネッセンス素子。以下、有機ＥＬ素子。）が知られている。有機ＥＬ素子は、一対の電極間に、発光層、電子輸送層、正孔輸送層等の複数種の層が積層された構成を基本構造としている。 Conventionally, an organic photoelectron element (organic electroluminescence element, hereinafter referred to as an organic EL element) is known as a self-luminous element. The basic structure of an organic EL element is such that a plurality of types of layers such as a light emitting layer, an electron transporting layer, and a hole transporting layer are laminated between a pair of electrodes.
　有機ＥＬ素子を構成する複数種の層の材料として、フッ素樹脂が用いられることがある。フッ素樹脂は、層を低屈折率化するための低屈折率材料、電極のバッファーなど、種々の目的で用いられている。
　例えば、フッ素樹脂を材料とする陽極バッファー層を有する有機ＥＬ素子が知られている（特許文献１参照）。特許文献１に記載の有機ＥＬ素子では、フッ素樹脂を蒸着させることにより、陽極バッファー層を形成している。 Fluororesin may be used as a material for a plurality of types of layers constituting an organic EL element. Fluororesin is used for various purposes such as a low refractive index material for lowering the refractive index of a layer and a buffer for an electrode.
For example, an organic EL device having an anode buffer layer made of a fluororesin is known (see Patent Document 1). In the organic EL device described in Patent Document 1, an anode buffer layer is formed by depositing a fluororesin.
中国特許第１００５５７８５２号明細書Chinese Patent No. 100575852
　特許文献１の実施例においては、真空チャンバー内において、減圧下フッ素樹脂を蒸着させることが記載されている。特許文献１の実施例では、成膜開始時に８×１０－３Ｐａであったチャンバー内圧力が、成膜終了時には１～３×１０－２Ｐａにまで上昇している。これは、用いたフッ素樹脂が蒸着条件において熱分解し、生じた低分子の分解物が気化することにより、チャンバー内圧力を上げていると考えられる。
　特許文献１に記載のように、蒸着中に熱分解してしまうフッ素樹脂を用いると、所望の蒸着条件を担保しにくいことが予想される。そのため、たとえ有機ＥＬ素子が得られたとしても、品質が安定しないおそれがあり、改善が求められていた。 In the embodiment of Patent Document 1, it is described that the fluororesin is vapor-deposited under reduced pressure in a vacuum chamber. In the example of Patent Document 1, the pressure in the chamber, which was 8 × 10 -3 Pa at the start of film formation, has increased to 1 to 3 × 10 -2 Pa at the end of film formation. It is considered that this is because the fluororesin used is thermally decomposed under the vapor deposition conditions, and the generated small molecule decomposition products are vaporized to increase the pressure in the chamber.
As described in Patent Document 1, when a fluororesin that thermally decomposes during vapor deposition is used, it is expected that it is difficult to secure desired vapor deposition conditions. Therefore, even if an organic EL element is obtained, the quality may not be stable, and improvement has been required.
　本発明はこのような事情に鑑みてなされたものであって、蒸着に適した含フッ素重合体を提供することを目的とする。また、このような含フッ素重合体を材料として含む膜を提供することを併せて目的とする。また、このような膜を容易に製造可能する膜の製造方法を提供することをあわせて目的とする。さらに、このような膜を構造に有する有機光電子素子を提供することを併せて目的とする。 The present invention has been made in view of such circumstances, and an object of the present invention is to provide a fluorine-containing polymer suitable for vapor deposition. Another object of the present invention is to provide a film containing such a fluorine-containing polymer as a material. Another object of the present invention is to provide a method for producing a film capable of easily producing such a film. Another object of the present invention is to provide an organic photoelectron element having such a film in its structure.
　上記の課題を解決するため、本発明は、以下の態様を包含する。
［１］下記（１）～（３）を満たす含フッ素重合体。
（１）融点が２００℃以上である。（２）１×１０－３Ｐａの圧力下において昇温速度２℃／分で昇温させたときの熱重量減少率が、４００℃以下で実質的に１００％に達する。（３）１×１０－３Ｐａの圧力下において昇温速度２℃／分で昇温させたとき、熱重量減少率が１０％となる温度から９０％になる温度までの温度幅が１００℃以内である。
［２］２５℃における貯蔵弾性率が１×１０７Ｐａ以上であり、降温速度２℃／分で降温させたときに変化する貯蔵弾性率が１×１０６Ｐａ未満になる温度は１２０℃以上である、［１］に記載の含フッ素重合体。
［３］フルオロオレフィンに由来する単位を有する、［１］または［２］に記載の含フッ素重合体。
［４］少なくともテトラフルオロエチレンに由来する単位を有する、［３］に記載の含フッ素重合体。
［５］ペルフルオロアルキルビニルエーテルに由来する単位を有する、［３］または［４］に記載の含フッ素重合体。
［６］前記ペルフルオロアルキルビニルエーテルがペルフルオロプロピルビニルエーテルである、［５］に記載の含フッ素重合体。 In order to solve the above problems, the present invention includes the following aspects.
[1] A fluorine-containing polymer that satisfies the following (1) to (3).
(1) The melting point is 200 ° C. or higher. (2) The thermogravimetric reduction rate when the temperature is raised at a heating rate of 2 ° C./min under a pressure of 1 × 10 -3 Pa reaches substantially 100% at 400 ° C. or lower. (3) When the temperature is raised at a heating rate of 2 ° C./min under a pressure of 1 × 10 -3 Pa, the temperature range from the temperature at which the thermogravimetric reduction rate is 10% to the temperature at which the temperature is 90% is 100 ° C. Within.
[2] The storage elastic modulus at 25 ° C. is 1 × 10 7 Pa or more, and the temperature at which the storage elastic modulus that changes when the temperature is lowered at a temperature lowering rate of 2 ° C./min is less than 1 × 10 6 Pa is 120 ° C. or more. The fluorine-containing polymer according to [1].
[3] The fluorine-containing polymer according to [1] or [2], which has a unit derived from a fluoroolefin.
[4] The fluorine-containing polymer according to [3], which has at least a unit derived from tetrafluoroethylene.
[5] The fluorine-containing polymer according to [3] or [4], which has a unit derived from perfluoroalkyl vinyl ether.
[6] The fluorine-containing polymer according to [5], wherein the perfluoroalkyl vinyl ether is a perfluoropropyl vinyl ether.
［７］前記［１］から［６］のいずれかに記載の含フッ素重合体と有機半導体とを含む膜。
［８］前記含フッ素重合体と前記有機半導体との合計に対する前記含フッ素重合体の割合が、２０～８０体積％である、［７］に記載の膜。
［９］ドーパントをさらに含む、［７］または［８］に記載の膜。
［１０］前記含フッ素重合体と前記有機半導体との共蒸着膜である、［１］から［９］のいずれかに記載の膜。
［１１］前記［１］から［６］のいずれかに記載の含フッ素重合体と有機半導体とを共蒸着させる工程を有する、膜の製造方法。
［１２］前記共蒸着させる工程において、ドーパントをあわせて共蒸着させる、［１１］に記載の膜の製造方法。 [7] A film containing the fluorine-containing polymer according to any one of [1] to [6] and an organic semiconductor.
[8] The film according to [7], wherein the ratio of the fluorine-containing polymer to the total of the fluorine-containing polymer and the organic semiconductor is 20 to 80% by volume.
[9] The film according to [7] or [8], further comprising a dopant.
[10] The film according to any one of [1] to [9], which is a co-deposited film of the fluorine-containing polymer and the organic semiconductor.
[11] A method for producing a film, which comprises a step of co-depositing the fluorine-containing polymer according to any one of [1] to [6] and an organic semiconductor.
[12] The method for producing a film according to [11], wherein in the step of co-depositing, a dopant is also co-deposited.
［１３］前記［７］から［１０］のいずれかに記載の膜を含む有機光電子素子。
［１４］基板と、前記基板に設けられた陽極と、前記陽極に対向する陰極と、前記陽極と前記陰極との間に配置された活性層と、前記活性層と前記陽極との間に配置された正孔輸送層と、前記正孔輸送層と前記陽極との間に配置された正孔注入層と、を備え、前記正孔輸送層および前記正孔注入層の少なくとも一方の層が前記膜である、［１３］に記載の有機光電子素子。
［１５］基板と、前記基板に設けられた陽極と、前記陽極に対向する陰極と、前記陽極と前記陰極との間に配置された活性層と、前記活性層と前記陰極との間に配置された電子輸送層と、前記電子輸送層と前記陰極との間に配置された電子注入層と、を備え、前記電子輸送層および前記電子注入層の少なくとも一方の層が前記膜である、［１３］または［１４］に記載の有機光電子素子。 [13] An organic photoelectron device including the film according to any one of [7] to [10].
[14] A substrate, an anode provided on the substrate, a cathode facing the anode, an active layer arranged between the anode and the anode, and an arrangement between the active layer and the anode. The hole transport layer and the hole injection layer arranged between the hole transport layer and the anode are provided, and at least one layer of the hole transport layer and the hole injection layer is said. The organic photoelectron element according to [13], which is a film.
[15] A substrate, an anode provided on the substrate, a cathode facing the anode, an active layer arranged between the anode and the cathode, and arranged between the active layer and the cathode. The electron transport layer and the electron injection layer arranged between the electron transport layer and the cathode are provided, and at least one layer of the electron transport layer and the electron injection layer is the film. 13] or the organic photoelectron element according to [14].
　本発明によれば、蒸着に適した含フッ素重合体を提供できる。また、このような含フッ素重合体を材料として含む膜を提供できる。また、このような膜を容易に製造可能する膜の製造方法を提供できる。さらに、このような膜を構造に有する有機光電子素子を提供できる。 According to the present invention, it is possible to provide a fluorine-containing polymer suitable for vapor deposition. Further, it is possible to provide a film containing such a fluorine-containing polymer as a material. Further, it is possible to provide a method for producing a film capable of easily producing such a film. Further, it is possible to provide an organic photoelectron element having such a film in its structure.
図１は、含フッ素重合体の要件（２）（３）を説明する模式図である。FIG. 1 is a schematic diagram illustrating the requirements (2) and (3) of the fluorine-containing polymer. 図２は、第１実施形態の膜を示す概略断面図である。FIG. 2 is a schematic cross-sectional view showing the film of the first embodiment. 図３は、膜１０を製造する工程を示す模式図である。FIG. 3 is a schematic view showing a process of manufacturing the film 10. 図４は、膜１０を製造する工程を示す模式図である。FIG. 4 is a schematic view showing a process of manufacturing the film 10. 図５は、膜１０を製造する工程を示す模式図である。FIG. 5 is a schematic view showing a process of manufacturing the film 10. 図６は、本発明の第２実施形態に係る有機光電子素子（有機ＥＬ素子）１００を示す断面模式図である。FIG. 6 is a schematic cross-sectional view showing an organic photoelectronic device (organic EL device) 100 according to a second embodiment of the present invention. 図７は、本発明の第３実施形態に係る有機ＥＬ素子２００の説明図である。FIG. 7 is an explanatory diagram of the organic EL element 200 according to the third embodiment of the present invention.
　本明細書における重合体を構成する「単位」とは、重合体中に存在して重合体を構成する、単量体１分子に由来する部分（すなわち、単量体単位）を意味する。以下、個々の単量体に由来する単位をその単量体名に「単位」を付した名称で呼ぶ場合がある。 The "unit" constituting the polymer in the present specification means a portion derived from one monomer molecule (that is, a monomer unit) that exists in the polymer and constitutes the polymer. Hereinafter, a unit derived from an individual monomer may be referred to by adding a "unit" to the monomer name.
　本明細書において重合体の「主鎖」とは、炭素－炭素不飽和二重結合を有する単量体の付加重合により生じる、単量体において炭素－炭素不飽和二重結合を構成していた炭素原子から構成される炭素原子鎖をいう。 In the present specification, the "main chain" of the polymer constitutes a carbon-carbon unsaturated double bond in the monomer generated by addition polymerization of the monomer having a carbon-carbon unsaturated double bond. A carbon atom chain composed of carbon atoms.
　本明細書における「脂肪族環」は、環骨格が炭素原子のみから構成される炭素環構造のものに加えて、環骨格に炭素原子以外の原子（ヘテロ原子）を含む複素環構造のものも意味する。ヘテロ原子としては酸素原子、窒素原子、硫黄原子等が挙げられる。 The "aliphatic ring" in the present specification includes not only a carbocyclic ring structure in which the ring skeleton is composed of only carbon atoms, but also a heterocyclic ring structure in which the ring skeleton contains atoms other than carbon atoms (heteroatoms). means. Examples of the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom and the like.
［第１実施形態］
　以下、図１～図５を参照しながら、本発明の第１実施形態に係る含フッ素重合体、膜、膜の製造方法について説明する。なお、以下の全ての図面においては、図面を見やすくするため、各構成要素の寸法や比率などは適宜異ならせてある。 [First Embodiment]
Hereinafter, a method for producing a fluorine-containing polymer, a membrane, and a membrane according to the first embodiment of the present invention will be described with reference to FIGS. 1 to 5. In all the drawings below, the dimensions and ratios of the components are appropriately different in order to make the drawings easier to see.
（含フッ素重合体）
　本実施形態の含フッ素重合体は、下記の要件（１）～（３）を満たす。
　要件（１）融点が２００℃以上である。
　要件（２）１×１０－３Ｐａの圧力下において昇温速度２℃／分で昇温させたときの熱重量減少率が、４００℃以下で実質的に１００％に達する。
　要件（３）１×１０－３Ｐａの圧力下において昇温速度２℃／分で昇温させたとき、熱重量減少率が１０％となる温度から９０％になる温度までの温度幅が１００℃以内である。 (Fluorine-containing polymer)
The fluorine-containing polymer of the present embodiment satisfies the following requirements (1) to (3).
Requirements (1) The melting point is 200 ° C or higher.
Requirement (2) The thermogravimetric reduction rate when the temperature is raised at a heating rate of 2 ° C./min under a pressure of 1 × 10 -3 Pa reaches substantially 100% at 400 ° C. or lower.
Requirement (3) When the temperature is raised at a heating rate of 2 ° C./min under a pressure of 1 × 10 -3 Pa, the temperature range from the temperature at which the thermogravimetric reduction rate becomes 10% to the temperature at which the temperature decreases to 90% is 100. It is within ° C.
　上記要件（１）～（３）を満たす含フッ素重合体は、蒸着に適した物性を有し、好適に蒸着膜を形成可能となる。
　以下、順に説明する。 Fluorine-containing polymers that satisfy the above requirements (1) to (3) have physical properties suitable for vapor deposition, and a vapor-deposited film can be suitably formed.
Hereinafter, they will be described in order.
（含フッ素重合体の構造）
　本実施形態の含フッ素重合体としては、高い結晶性を有し、所望の範囲の融点を有する重合体であれば単位に特に制限はない。 (Structure of fluorine-containing polymer)
The unit of the fluorine-containing polymer of the present embodiment is not particularly limited as long as it has high crystallinity and a melting point in a desired range.
　含フッ素重合体は、フルオロオレフィンに由来する単位を有する重合体が好ましい。より具体的には、含フッ素重合体は、少なくともテトラフルオロエチレン（ＴＦＥ）に由来する単位（すなわち、ＴＦＥ単位）を有することが好ましい。 The fluorine-containing polymer is preferably a polymer having a unit derived from a fluoroolefin. More specifically, the fluorine-containing polymer preferably has at least a unit derived from tetrafluoroethylene (TFE) (that is, a TFE unit).
　含フッ素重合体は、一般に、ＴＦＥ単位や、クロロトリフルオロエチレン（ＣＴＦＥ）に由来する単位（すなわち、ＣＴＦＥ単位）を高い比率で含有すると、高い結晶性を得られることが知られている。そのため、本実施形態の含フッ素重合体も、ＴＦＥ単位や、ＣＴＦＥ単位を高い比率で含有することが好ましい。 It is generally known that a fluorine-containing polymer can obtain high crystallinity when it contains a TFE unit or a unit derived from chlorotrifluoroethylene (CTFE) (that is, a CTFE unit) in a high ratio. Therefore, it is preferable that the fluorine-containing polymer of the present embodiment also contains TFE units and CTFE units in a high ratio.
　含フッ素重合体全体に対するＴＦＥ単位およびＣＴＦＥ単位の割合は、５０ｍｏｌ％以上であることが好ましく、７０ｍｏｌ％以上であることがより好ましく、９０ｍｏｌ％以上であることがさらに好ましい。含フッ素重合体が、ＴＦＥ単位とＣＴＦＥ単位との両方を含む場合は、ＴＦＥ単位の割合と、ＣＴＦＥ単位の割合との和が、上記含有率以上であると好ましい。
　上記含有率の上限値は、１００ｍｏｌ％である。 The ratio of the TFE unit and the CTFE unit to the entire fluorine-containing polymer is preferably 50 mol% or more, more preferably 70 mol% or more, and further preferably 90 mol% or more. When the fluorine-containing polymer contains both TFE units and CTFE units, it is preferable that the sum of the ratio of TFE units and the ratio of CTFE units is equal to or greater than the above-mentioned content ratio.
The upper limit of the content rate is 100 mol%.
　本実施形態の含フッ素重合体は、ＴＦＥまたはＣＴＦＥの単独重合体でもよく、ＴＦＥまたはＣＴＦＥと他の単量体とからなる群から選ばれる２種以上の単量体の共重合体であってもよい。
　上記他の単量体は、ＴＦＥまたはＣＴＦＥと共重合可能であれば特に制限はない。他の単量体は、炭化水素系単量体でもよく、含フッ素単量体でもよい。 The fluoropolymer of the present embodiment may be a homopolymer of TFE or CTFE, and is a copolymer of two or more kinds of monomers selected from the group consisting of TFE or CTFE and other monomers. May be good.
The other monomer is not particularly limited as long as it can be copolymerized with TFE or CTFE. The other monomer may be a hydrocarbon-based monomer or a fluorine-containing monomer.
　上記他の単量体としての炭化水素系単量体としては、例えば、エチレン、プロピレン、スチレン等の炭化水素系単量体が挙げられる。
　他の単量体として炭化水素系単量体を用いる場合、含フッ素重合体の全単位に対する、他の単量体に由来する単位の割合は、５０ｍｏｌ％以下であることが好ましく、３０ｍｏｌ％以下であることがより好ましく、１０ｍｏｌ％以下であることがさらに好ましい。 Examples of the hydrocarbon-based monomer as the other monomer include hydrocarbon-based monomers such as ethylene, propylene, and styrene.
When a hydrocarbon-based monomer is used as the other monomer, the ratio of the units derived from the other monomer to all the units of the fluorine-containing polymer is preferably 50 mol% or less, preferably 30 mol% or less. Is more preferable, and 10 mol% or less is further preferable.
　得られる含フッ素重合体の屈折率が相対的に小さくなるため、上記他の単量体としては、含フッ素単量体が好ましい。含フッ素単量体としては、ペルフルオロ化合物が好ましい。
　他の単量体である含フッ素単量体としては、重合により主鎖に脂肪族環構造を有する単位となる単量体であってもよいが、このような含フッ素重合体の主鎖に脂肪族環構造をもたらす単量体ではないことが好ましい。主鎖に脂肪族環構造を有しない含フッ素重合体は、主鎖に脂肪族環構造を有する含フッ素重合体と比較して結晶性が高く、含フッ素重合体の融点を所望の範囲に制御しやすい。
　重合により主鎖に脂肪族環構造を有する単位となる単量体としては、後述のペルフルオロ環状モノエンや環化重合し得るペルフルオロジエンが挙げられる。
　ペルフルオロ化合物以外の含フッ素単量体としては、例えば、トリフルオロエチレン（ＴｒＦＥ）、ビニリデンフルオライド（ＶｄＦ）、１，２－ジフルオロエチレン、１－フルオロエチレン等が挙げられる。 Since the refractive index of the obtained fluorine-containing polymer is relatively small, the fluorine-containing monomer is preferable as the other monomer. As the fluorine-containing monomer, a perfluoro compound is preferable.
The fluorine-containing monomer, which is another monomer, may be a monomer that becomes a unit having an aliphatic ring structure in the main chain by polymerization, but the main chain of such a fluorine-containing polymer may be used. It is preferably not a monomer that provides an aliphatic ring structure. The fluorinated polymer having no aliphatic ring structure in the main chain has higher crystallinity than the fluorinated polymer having an aliphatic ring structure in the main chain, and the melting point of the fluorinated polymer is controlled within a desired range. It's easy to do.
Examples of the monomer that becomes a unit having an aliphatic ring structure in the main chain by polymerization include perfluorocyclic monoene and perfluorodiene that can be cyclized and polymerized, which will be described later.
Examples of the fluorine-containing monomer other than the perfluoro compound include trifluoroethylene (TrFE), vinylidene fluoride (VdF), 1,2-difluoroethylene, 1-fluoroethylene and the like.
　含フッ素単量体のうちペルフルオロ化合物としては、例えば、下記の、ペルフルオロオレフィン、ペルフルオロアルキルビニルエーテル、ペルフルオロ環状モノエン、環化重合し得るペルフルオロジエン等が挙げられる。
　ペルフルオロオレフィン：ヘキサフルオロプロペン（ＨＦＰ）等
　ペルフルオロアルキルビニルエーテル：ペルフルオロメチルビニルエーテル（ＰＭＶＥ）、ペルフルオロエチルビニルエーテル（ＰＥＶＥ）、ペルフルオロプロピルビニルエーテル（ＰＰＶＥ）等
　ペルフルオロ環状モノエン：ペルフルオロ（４－メトキシ－１，３－ジオキソール）、ペルフルオロ（２，２－ジメチル－１，３－ジオキソール）、ペルフルオロ（４-メチル－２－メチレン－１，３－ジオキソラン）等
　環化重合し得るペルフルオロジエン：ペルフルオロ（３－ブテニルビニルエーテル）等 Examples of the perfluoro compound among the fluorine-containing monomers include the following perfluoroolefins, perfluoroalkyl vinyl ethers, perfluorocyclic monoenes, perfluorodienes capable of cyclization polymerization, and the like.
Perfluoroolefin: hexafluoropropene (HFP), etc. Perfluoroalkyl vinyl ether: perfluoromethyl vinyl ether (PMVE), perfluoroethyl vinyl ether (PEVE), perfluoropropyl vinyl ether (PPVE), etc. Perfluorocyclic monoene: perfluoro (4-methoxy-1,3-dioxol) ), Perfluoro (2,2-dimethyl-1,3-dioxol), Perfluoro (4-methyl-2-methylene-1,3-dioxolane), etc. Perfluorodiene capable of cyclization polymerization: Perfluoro (3-butenyl vinyl ether) etc
　なかでも、含フッ素重合体としては、ペルフルオロアルキルビニルエーテル単位を有することが好ましい。特に、含フッ素重合体は、ＰＰＶＥ単位を有することが好ましい。
　含フッ素重合体は、ＰＰＶＥ単位の含有率が変化すると、融点が変化する。具体的には、含フッ素重合体に対するＰＰＶＥ単位の含有率が増えると、含フッ素重合体の融点が下がる傾向にある。 Among them, the fluorine-containing polymer preferably has a perfluoroalkyl vinyl ether unit. In particular, the fluorine-containing polymer preferably has PPVE units.
The melting point of the fluorine-containing polymer changes when the content of PPVE units changes. Specifically, as the content of PPVE units with respect to the fluorine-containing polymer increases, the melting point of the fluorine-containing polymer tends to decrease.
　含フッ素重合体に対するＰＰＶＥ単位の含有率は、１４ｍｏｌ％未満が好ましく、１０ｍｏｌ％以下がより好ましい。
　含フッ素重合体に対するＰＰＶＥ単位の含有率は、上限は特に制限されないが、０ｍｏｌ％を超えることが好ましく、１ｍｏｌ％以上がより好ましい。
　含フッ素重合体に対するＰＰＶＥ単位の含有率について、上限値と下限値とは、任意に組み合わせることができる。例えば、上記含有率は、１～１２ｍｏｌ％が好ましい。 The content of PPVE units with respect to the fluorine-containing polymer is preferably less than 14 mol%, more preferably 10 mol% or less.
The upper limit of the content of PPVE units with respect to the fluorine-containing polymer is not particularly limited, but is preferably more than 0 mol%, more preferably 1 mol% or more.
Regarding the content of PPVE units with respect to the fluorine-containing polymer, the upper limit value and the lower limit value can be arbitrarily combined. For example, the content is preferably 1 to 12 mol%.
　上述した各単量体は、通常、ラジカル重合開始剤を用いたラジカル重合により重合される。この場合、重合終了時の含フッ素重合体は、分子鎖（主鎖）の末端の構造が、重合で用いたラジカル重合開始剤のフラグメントが付加した構造であることが考えられる。また、重合に際して連鎖移動剤を用いた場合、分子鎖（主鎖）の末端の構造は、連鎖移動剤のフラグメントが付加した構造を取り得る。
　含フッ素重合体は、上記末端の構造が他の構造に変換されてもよい。例えば、上述した重合終了時の含フッ素重合体について３００℃以上に熱処理することにより、主鎖の末端の構造は、－Ｃ（＝Ｏ）－Ｆとなり、含フッ素重合体は酸フッ化物となる。 Each of the above-mentioned monomers is usually polymerized by radical polymerization using a radical polymerization initiator. In this case, it is considered that the structure at the end of the molecular chain (main chain) of the fluoropolymer at the end of polymerization is a structure to which a fragment of the radical polymerization initiator used in the polymerization is added. When a chain transfer agent is used in the polymerization, the structure at the end of the molecular chain (main chain) can be a structure to which a fragment of the chain transfer agent is added.
In the fluorine-containing polymer, the terminal structure may be converted into another structure. For example, by heat-treating the above-mentioned fluorine-containing polymer at the end of polymerization to 300 ° C. or higher, the structure at the end of the main chain becomes -C (= O) -F, and the fluorine-containing polymer becomes acid fluoride. ..
　上記酸フッ化物をメタノール処理することにより、主鎖の末端の構造は、メチルエステル基となる。メチルエステル基は、簡便なメタノール処理により、反応性が高い酸フッ化物から変換可能である。そのため、得られる含フッ素重合体の安定性を向上させやすいため好ましい。 By treating the acid fluoride with methanol, the structure at the end of the main chain becomes a methyl ester group. The methyl ester group can be converted from a highly reactive acid fluoride by a simple methanol treatment. Therefore, it is preferable because the stability of the obtained fluorine-containing polymer can be easily improved.
　さらに、上記酸フッ化物をフッ化処理することで、主鎖の末端の構造は、トリフルオロメチル基となる。フッ化処理としては、例えば、特開平１１－１５２３１０号公報の段落００４０に記載された処理方法を挙げることができる。トリフルオロメチル基は、耐熱性が高く、得られる含フッ素重合体の耐熱性が向上しやすいため好ましい。
　また、含フッ素重合体は、主鎖の末端の構造がメチルエステル基やトリフルオロメチル基であると、主鎖の末端における分子間相互作用が小さく、蒸着しやすくなるため好ましい。
　上述した主鎖の末端の構造は、赤外線分光分析により確認できる。 Further, by fluorinating the acid fluoride, the structure at the end of the main chain becomes a trifluoromethyl group. Examples of the fluorination treatment include the treatment method described in paragraph 0040 of JP-A-11-152310. The trifluoromethyl group is preferable because it has high heat resistance and the heat resistance of the obtained fluorine-containing polymer can be easily improved.
Further, in the fluorine-containing polymer, when the structure at the end of the main chain is a methyl ester group or a trifluoromethyl group, the intermolecular interaction at the end of the main chain is small and vapor deposition is easy, which is preferable.
The structure at the end of the main chain described above can be confirmed by infrared spectroscopic analysis.
（要件（１））
　本実施形態の含フッ素重合体は、結晶性を有することが好ましい。含フッ素重合体が結晶性を有すことにより、融点が２００℃以上となりやすい。本実施形態の含フッ素重合体の融点は、２１５℃以上が好ましく、２２５℃以上がより好ましく、２４０℃以上がさらに好ましい。
　また、本実施形態の含フッ素重合体の融点は、上限は特に制限されないが、３５０℃以下であることが好ましく、３２０℃以下であることがより好ましく、３００℃以下がさらに好ましい。
　含フッ素重合体の融点の上限値と下限値とは、任意に組み合わせることができる。例えば、含フッ素重合体の融点は、２００～３５０℃であってもよく、２１５～３２０℃であってもよく、２２５～３００℃であってもよい。 (Requirement (1))
The fluorine-containing polymer of the present embodiment preferably has crystallinity. Since the fluorine-containing polymer has crystallinity, the melting point tends to be 200 ° C. or higher. The melting point of the fluorine-containing polymer of the present embodiment is preferably 215 ° C. or higher, more preferably 225 ° C. or higher, and even more preferably 240 ° C. or higher.
The upper limit of the melting point of the fluorine-containing polymer of the present embodiment is not particularly limited, but is preferably 350 ° C. or lower, more preferably 320 ° C. or lower, and even more preferably 300 ° C. or lower.
The upper limit value and the lower limit value of the melting point of the fluorine-containing polymer can be arbitrarily combined. For example, the melting point of the fluorine-containing polymer may be 200 to 350 ° C., 215 to 320 ° C., or 225 to 300 ° C.
　本実施形態において、融点は、示差走査熱量計（例えば、ＮＥＴＺＳＣＨ製：ＤＳＣ　２０４　Ｆ１　Ｐｈｏｅｎｉｘ）を用いて測定する値を採用する。含フッ素重合体９ｍｇを試料容器に仕込み、－７０℃から３５０まで毎分１０℃で昇温させた際の熱容量を測定し、得られた融解ピークより融点を求める。 In the present embodiment, the melting point adopts a value measured using a differential scanning calorimeter (for example, manufactured by NETZSCH: DSC 204 F1 Phoenix). 9 mg of the fluorine-containing polymer is charged in a sample container, the heat capacity when the temperature is raised from −70 ° C. to 350 at 10 ° C. per minute is measured, and the melting point is determined from the obtained melting peak.
（要件（２））
　本実施形態において、熱重量減少率は、真空示差熱天秤（アドバンス理工社製：ＶＰＥ－９０００）を用いて測定する値を採用する。具体的には、含フッ素重合体５０ｍｇを内径７ｍｍのセルに仕込み、１×１０－３Ｐａの真空度にて、室温から５００℃まで毎分２℃で昇温させた際の、含フッ素重合体の初期重量（５０ｍｇ）に対する重量減少率（％）を測定する。 (Requirement (2))
In the present embodiment, the thermogravimetric reduction rate adopts a value measured using a vacuum differential thermal balance (manufactured by Advance Riko Co., Ltd .: VPE-9000). Specifically, the fluorine-containing weight when 50 mg of the fluorine-containing polymer was charged into a cell having an inner diameter of 7 mm and the temperature was raised from room temperature to 500 ° C. at 2 ° C. per minute at a vacuum degree of 1 × 10 -3 Pa. The weight loss rate (%) with respect to the initial weight (50 mg) of the coalescence is measured.
　要件（２）における「実質的に」とは、上述した熱重量減少率の測定方法において、４００℃を超えた温度範囲での熱重量減少が検出下限を下回っており、熱重量減少が確認できないことを意味する。 “Substantially” in the requirement (2) means that in the above-mentioned method for measuring the thermogravimetric rate, the thermogravimetric decrease in the temperature range exceeding 400 ° C. is below the lower limit of detection, and the thermogravimetric decrease cannot be confirmed. Means that.
　本実施形態の含フッ素重合体は、上記要件（２）を満たす温度が低いほど分子量（重合度）が低いということができる。上記要件（２）を満たさない含フッ素重合体を蒸着させようと、４００℃を超えた温度範囲での加熱を試みると、含フッ素重合体が熱分解するおそれがある。その場合、熱分解で生じた生成物が、蒸着で用いる真空チャンバーの内部圧力を上昇させるおそれがある。このように、真空チャンバーの内部圧力が上昇すると、蒸着条件が不安定となり、蒸着膜の品質が安定しないおそれがある。また、部分的に熱分解した含フッ素重合体が蒸着膜中に混入し、蒸着膜の品質が損なわれるおそれがある。 It can be said that the lower the temperature at which the fluorine-containing polymer of the present embodiment satisfies the above requirement (2), the lower the molecular weight (degree of polymerization). If an attempt is made to heat a fluorinated polymer that does not satisfy the above requirement (2) in a temperature range exceeding 400 ° C., the fluorinated polymer may be thermally decomposed. In that case, the product produced by thermal decomposition may increase the internal pressure of the vacuum chamber used for vapor deposition. When the internal pressure of the vacuum chamber rises in this way, the vapor deposition conditions become unstable, and the quality of the vapor deposition film may not be stable. In addition, the partially thermally decomposed fluorine-containing polymer may be mixed in the vapor-deposited film, and the quality of the vapor-deposited film may be impaired.
　一方、上記要件（２）を満たす含フッ素重合体は、真空下で行う蒸着材料として用いたとき、４００℃よりも低い温度で加熱することで、好適に蒸着させることが可能となる。これにより、上述した熱分解のおそれがなく、安定した蒸着条件で蒸着処理が可能となる。 On the other hand, when the fluorine-containing polymer satisfying the above requirement (2) is used as a vapor deposition material performed under vacuum, it can be suitably vapor-deposited by heating at a temperature lower than 400 ° C. As a result, there is no risk of thermal decomposition described above, and the vapor deposition process can be performed under stable vapor deposition conditions.
　含フッ素重合体の耐熱性は、真空チャンバーの内部圧力の変化に着目すると、以下のように評価できる。 The heat resistance of the fluorine-containing polymer can be evaluated as follows, focusing on the change in the internal pressure of the vacuum chamber.
［蒸着時のチャンバー圧変化の評価法］
　真空蒸着機に含フッ素重合体を０．１g仕込み、チャンバー内の圧力を１０－４Ｐａ以下に減圧した上で、含フッ素重合体を蒸着速度０．１ｎｍ／秒で２００ｎｍ成膜する。この際にチャンバー内の圧力をモニターし、蒸着時における圧力の最大値を計測する。
　下記計算式より求められるチャンバー圧力の上昇倍率が２倍以下の含フッ素重合体は、好適に蒸着させることが可能となる。
　蒸着時のチャンバー圧力の上昇倍率＝蒸着中の最大圧力／蒸着前の初期圧力 [Evaluation method of chamber pressure change during vapor deposition]
0.1 g of the fluorine-containing polymer is charged into a vacuum vapor deposition machine, the pressure in the chamber is reduced to 10 -4 Pa or less, and then the fluorine-containing polymer is deposited at a vapor deposition rate of 0.1 nm / sec to 200 nm. At this time, the pressure in the chamber is monitored and the maximum value of the pressure at the time of vapor deposition is measured.
A fluorine-containing polymer having a chamber pressure increase rate of 2 times or less, which is obtained from the following formula, can be suitably vapor-deposited.
Increase rate of chamber pressure during vapor deposition = maximum pressure during vapor deposition / initial pressure before vapor deposition
　上昇倍率が２倍を超える含フッ素重合体は、熱分解が進みやすく、蒸着に用いるには不適と判断できる。
　さらに、チャンバー圧力の上昇倍率が１０倍を超えるほど含フッ素重合体が熱分解する場合、熱分解で生じた生成物により、製造する蒸着膜の品質が安定しないおそれがある。 A fluorine-containing polymer having an increase ratio of more than 2 times is likely to undergo thermal decomposition and can be judged to be unsuitable for use in vapor deposition.
Further, when the fluorine-containing polymer is thermally decomposed so that the increase ratio of the chamber pressure exceeds 10 times, the quality of the vapor-deposited film to be produced may not be stable due to the product produced by the thermal decomposition.
　本実施形態の含フッ素重合体は、１×１０－３Ｐａの圧力下において昇温速度２℃／分で昇温させたときの熱重量減少率が、３５０℃以下で実質的に１００％に達することが好ましい。 The fluorine-containing polymer of the present embodiment has a thermogravimetric reduction rate of substantially 100% at 350 ° C. or lower when the temperature is raised at a heating rate of 2 ° C./min under a pressure of 1 × 10 -3 Pa. It is preferable to reach.
（要件（３））
　本実施形態の含フッ素重合体は、１×１０－３Ｐａの圧力下において昇温速度２℃／分で昇温させたとき、熱重量減少率が１０％となる温度から９０％になる温度までの温度幅が１００℃以内である。 (Requirement (3))
The fluorine-containing polymer of the present embodiment has a temperature at which the thermogravimetric reduction rate changes from 10% to 90% when the temperature is raised at a temperature rising rate of 2 ° C./min under a pressure of 1 × 10 -3 Pa. The temperature range up to is within 100 ° C.
　本実施形態の含フッ素重合体は、上記要件（３）を満たす温度幅が狭いほど分子量分布が狭いということができる。
　上記要件（３）を満たさない含フッ素重合体を用い蒸着膜を製造しようとすると、蒸着の始期に蒸着される含フッ素重合体の分子量と、蒸着の終期に蒸着される含フッ素重合体の分子量との差が大きく、同じ蒸着膜において、蒸着膜の厚み方向で含フッ素重合体の分子量が変化し、蒸着膜の物性が安定しないおそれがある。
　また、同条件で連続的に蒸着膜を製造する場合、上記要件（３）を満たさない含フッ素重合体を用いると、製造される蒸着膜の品質がロット間でばらつくおそれがある。
　このように、要件（３）を満たさない含フッ素重合体を用いると、蒸着条件が不安定となり、蒸着膜の品質が安定しないおそれがある。 It can be said that the fluorinated polymer of the present embodiment has a narrower molecular weight distribution as the temperature range satisfying the above requirement (3) is narrower.
When an attempt is made to produce a vapor-deposited film using a fluorine-containing polymer that does not satisfy the above requirement (3), the molecular weight of the fluorine-containing polymer deposited at the beginning of vapor deposition and the molecular weight of the fluorine-containing polymer deposited at the end of vapor deposition. In the same vapor-deposited film, the molecular weight of the fluorine-containing polymer changes in the thickness direction of the thin-film film, and the physical properties of the thin-film film may not be stable.
Further, when the vapor-deposited film is continuously produced under the same conditions, if a fluorine-containing polymer that does not satisfy the above requirement (3) is used, the quality of the produced film-deposited film may vary from lot to lot.
If a fluorine-containing polymer that does not satisfy the requirement (3) is used as described above, the vapor deposition conditions may become unstable and the quality of the vapor deposition film may not be stable.
　一方、上記要件（３）を満たす含フッ素重合体は、蒸着の始期に蒸着される含フッ素重合体の分子量と、蒸着の終期に蒸着される含フッ素重合体の分子量との差が小さく、蒸着膜の厚み方向において含フッ素重合体の分子量の変化が小さい。そのため、得られる蒸着膜の物性が安定しやすい。
　また、同条件で連続的に蒸着膜を製造する場合、製造される蒸着膜のロット間の品質ばらつきを抑制できる。
　これらにより、要件（３）を満たす含フッ素重合体を用いると、蒸着膜の品質が安定しやすい。 On the other hand, in the fluorine-containing polymer satisfying the above requirement (3), the difference between the molecular weight of the fluorine-containing polymer deposited at the beginning of vapor deposition and the molecular weight of the fluorine-containing polymer deposited at the end of vapor deposition is small, and the vapor deposition is carried out. The change in the molecular weight of the fluorine-containing polymer is small in the thickness direction of the film. Therefore, the physical characteristics of the obtained thin-film film are likely to be stable.
Further, when the vapor-deposited film is continuously produced under the same conditions, it is possible to suppress quality variation between lots of the produced vapor-film film.
Therefore, when a fluorine-containing polymer satisfying the requirement (3) is used, the quality of the vapor-deposited film is likely to be stable.
　本実施形態の含フッ素重合体は、１×１０－３Ｐａの圧力下において昇温速度２℃／分で昇温させたとき、熱重量減少率が１０％となる温度から９０％になる温度までの温度幅が７０℃以内であることが好ましい。 The fluorine-containing polymer of the present embodiment has a temperature at which the thermogravimetric reduction rate changes from 10% to 90% when the temperature is raised at a temperature rising rate of 2 ° C./min under a pressure of 1 × 10 -3 Pa. The temperature range up to is preferably 70 ° C. or less.
　図１は、要件（２）（３）を説明する模式図であり、測定温度に対する熱重量減少率の対応関係を示すグラフである。図１の横軸は測定温度（単位：℃）、縦軸は熱重量減少率（単位％）である。図１においては、要件（２）（３）を満たす含フッ素重合体の挙動を符号Ｐで示し、要件（２）（３）を満たさない含フッ素重合体の挙動を符号Ｐｘで示す。 FIG. 1 is a schematic diagram for explaining the requirements (2) and (3), and is a graph showing the correspondence relationship between the thermogravimetric reduction rate and the measured temperature. The horizontal axis of FIG. 1 is the measurement temperature (unit: ° C.), and the vertical axis is the thermogravimetric reduction rate (unit:%). In FIG. 1, the behavior of the fluorinated polymer satisfying the requirements (2) and (3) is indicated by reference numeral P, and the behavior of the fluorinated polymer not satisfying the requirements (2) and (3) is indicated by reference numeral Px.
　図１においては、本実施形態の含フッ素重合体の挙動について示すグラフＰは、４００℃よりも低い温度（Ｔｄ１００）で熱重量減少率が１００％に達している。対して、要件（２）（３）を満たさない含フッ素重合体の挙動について示すグラフＰｘは、４００℃において熱重量減少率が１００％に達していない。
　また、図１において、本実施形態の含フッ素重合体の挙動について示すグラフＰは、Ｔｄ９０－Ｔｄ１０の値Ｗが１００℃以下である。
　図１からは、本実施形態の含フッ素重合体は、温度Ｔｄ１０と温度Ｔｄ９０との間で急峻に熱重量減少を生じることが分かる。 In FIG. 1, the graph P showing the behavior of the fluorine-containing polymer of the present embodiment shows that the thermogravimetric reduction rate reaches 100% at a temperature (T d100) lower than 400 ° C. On the other hand, in the graph Px showing the behavior of the fluorine-containing polymer that does not satisfy the requirements (2) and (3), the thermogravimetric reduction rate does not reach 100% at 400 ° C.
Further, in FIG. 1, in the graph P showing the behavior of the fluorine-containing polymer of the present embodiment, the value W of T d90- T d10 is 100 ° C. or less.
From FIG. 1, it can be seen that the fluorine-containing polymer of the present embodiment causes a sharp decrease in thermogravimetric analysis between the temperature T d10 and the temperature T d90.
（分子量分画）
　上記要件（２）（３）を満たす含フッ素重合体は、重合体を分子量分画することで得られる。以下の説明では、分子量分画の対象となる重合体を、「原料重合体」と称することがある。
　分子量分画の方法としては、例えば、昇華精製や超臨界抽出により、分子量を分画し、要件（２）（３）を満たす重合体に調整する方法が挙げられる。 (Molecular weight fraction)
A fluorine-containing polymer satisfying the above requirements (2) and (3) can be obtained by fractionating the molecular weight of the polymer. In the following description, the polymer subject to molecular weight fractionation may be referred to as a "raw material polymer".
Examples of the method of molecular weight fractionation include a method of fractionating the molecular weight by sublimation purification or supercritical extraction to prepare a polymer satisfying the requirements (2) and (3).
（昇華精製）
　昇華精製は、減圧下で精製対象物（原料重合体）を加熱して精製対象物の一部または全部を昇華または蒸発させた後に、気体状態の精製対象物に含まれる化合物の析出温度差を利用して、目的の化合物を固体として分離し、回収する手法である。このような昇華精製は、精製対象物を仕込む仕込み部と、気体状態の精製対象物を析出温度ごとに分離して固体として捕集する捕集部を有し、かつ高い真空度を保つことのできる昇華精製装置を用いて行うことができる。
　昇華精製装置の構造は特に限定されないが、例えばガラス製の冷却管と冷却管を囲うフラスコ状のガラス容器と、ガラス容器の内部を減圧する真空排気装置からなる、いわゆるミル氏式の昇華精製装置を用いることができる。また、昇華精製装置としては、円筒状のガラス製の昇華管と、昇華管を内部に収容して昇華管を加熱する加熱装置と、昇華管の内部を減圧する高真空排気装置と、を備えたガラスチューブ式の昇華精製装置を用いることもできる。
　以下、ガラスチューブ式の昇華精製装置を例に、含フッ素重合体の昇華精製および昇華精製による分子量の分画方法を説明する。 (Sublimation purification)
In sublimation purification, the purification target (raw material polymer) is heated under reduced pressure to sublimate or evaporate a part or all of the purification target, and then the precipitation temperature difference of the compound contained in the purification target in a gaseous state is measured. This is a method for separating and recovering a target compound as a solid. Such sublimation purification has a charging section for charging the object to be purified and a collecting section for separating the purified object in a gaseous state at each precipitation temperature and collecting it as a solid, and maintains a high degree of vacuum. It can be carried out using a sublimation purification apparatus capable of this.
The structure of the sublimation purification device is not particularly limited, but for example, a so-called Mill-type sublimation purification device consisting of a glass cooling tube, a flask-shaped glass container surrounding the cooling tube, and a vacuum exhaust device for depressurizing the inside of the glass container. Can be used. Further, the sublimation refining device includes a cylindrical glass sublimation tube, a heating device that houses the sublimation tube inside to heat the sublimation tube, and a high vacuum exhaust device that depressurizes the inside of the sublimation tube. A glass tube type sublimation purification device can also be used.
Hereinafter, a method for sublimation purification of a fluorine-containing polymer and a method for fractionating the molecular weight by sublimation purification will be described using a glass tube type sublimation purification apparatus as an example.
　含フッ素重合体の昇華精製では、昇華管の仕込み部に原料重合体を仕込み、高真空排気装置を用いて、例えば、圧力を１×１０－３Ｐａ以下まで昇華管内の真空度を上げた後、加熱装置を用いて仕込み部を加熱する。これにより、原料重合体に含まれる含フッ素重合体が昇華または蒸発する。
　昇華管のうち、仕込み部よりも高真空排気装置による排気側にあたる領域は、「捕集部」に該当する。捕集部は、仕込み部の加熱温度よりも低い温度に設定されている。仕込み部で原料重合体から昇華または蒸発させた含フッ素重合体は、捕集部の壁面で析出し固化して、捕集される。 In the sublimation purification of the fluorine-containing polymer, the raw material polymer is charged in the preparation part of the sublimation tube, and the vacuum degree in the sublimation tube is raised to, for example, 1 × 10 -3 Pa or less by using a high vacuum exhaust device. , The preparation part is heated using a heating device. As a result, the fluorine-containing polymer contained in the raw material polymer is sublimated or evaporated.
Of the sublimation pipes, the area corresponding to the exhaust side of the high vacuum exhaust device from the preparation part corresponds to the "collection part". The collecting part is set to a temperature lower than the heating temperature of the charging part. The fluorine-containing polymer sublimated or evaporated from the raw material polymer in the charging section is precipitated and solidified on the wall surface of the collecting section and collected.
　捕集部の捕集温度は、含フッ素重合体が気体から固体へ昇華する温度（析出する温度）に対応し、含フッ素重合体の分子量に対応する。昇華管において捕集温度を異ならせた複数の捕集部を設けることにより、原料重合体を、分子量の異なる含フッ素重合体に分画できる。
　例えば、具体的には、仕込み部をＡ℃に加熱し、捕集部を仕込み部に近い側からＢ℃とＣ℃とに加熱した場合（Ａ＞Ｂ＞Ｃ）、Ｂ℃に設定した捕集部では、Ａ℃では気体、Ｂ℃では固体となる分子量範囲の含フッ素重合体が捕集される。
　同様に、Ｃ℃に設定した捕集部では、Ｂ℃では気体、Ｃ℃では固体となる分子量範囲の含フッ素重合体が捕集される。すなわち、Ｃ℃に設定した捕集部では、原料重合体に含まれる含フッ素重合体のうち、Ｂ℃では気体でありＣ℃では固体となる捕集温度幅Ｂ℃－Ｃ℃の含フッ素重合体が捕集される。 The collection temperature of the collection unit corresponds to the temperature at which the fluorine-containing polymer sublimates from a gas to a solid (the temperature at which it precipitates), and corresponds to the molecular weight of the fluorine-containing polymer. By providing a plurality of collection portions having different collection temperatures in the sublimation tube, the raw material polymer can be fractionated into fluorine-containing polymers having different molecular weights.
For example, specifically, when the charging portion is heated to A ° C. and the collecting portion is heated to B ° C. and C ° C. from the side closer to the charging portion (A>B> C), the trapping portion is set to B ° C. At the collecting part, a fluorine-containing polymer having a molecular weight range that becomes a gas at A ° C and a solid at B ° C is collected.
Similarly, in the collection section set to C ° C, a fluorine-containing polymer in a molecular weight range that becomes a gas at B ° C and a solid at C ° C is collected. That is, in the collection section set to C ° C., among the fluorine-containing polymers contained in the raw material polymer, the fluorine-containing weight having a collection temperature range of B ° C.—C ° C. which is a gas at B ° C. and a solid at C ° C. The coalescence is collected.
　上述の要件（３）は、上述のように捕集温度幅を制御し、例えば捕集温度幅１００℃となる捕集部で捕集することで満たすことができる。なお、捕集した含フッ素重合体について、要件（３）を満たすか否かを確認し、要件（３）を満たさない場合には、捕集部の温度条件を制御し、捕集温度幅を狭くするとよい。
　捕集部において、低い設定温度の領域で捕集された含フッ素重合体ほど、１×１０－３Ｐａの圧力下における熱重量減少率が１００％に達する温度が低い、すなわち分子量が小さい含フッ素重合体となる。 The above-mentioned requirement (3) can be satisfied by controlling the collection temperature range as described above, for example, by collecting in a collection section having a collection temperature range of 100 ° C. It should be noted that it is confirmed whether or not the collected fluorine-containing polymer satisfies the requirement (3), and if the requirement (3) is not satisfied, the temperature condition of the collecting portion is controlled and the collecting temperature range is adjusted. It is good to narrow it.
In the collection section, the fluorine-containing polymer collected in the lower set temperature region has a lower temperature at which the thermogravimetric reduction rate reaches 100% under a pressure of 1 × 10 -3 Pa, that is, has a smaller molecular weight. It becomes a polymer.
　捕集温度幅は、１００℃以下であることが好ましく、７０℃以下であることがより好ましく、４０℃以下であることがさらに好ましい。捕集温度幅が小さいほど、蒸着条件の変動が少なくなり、また、膜厚方向において均質な相分離構造が形成されやすい。 The collection temperature range is preferably 100 ° C. or lower, more preferably 70 ° C. or lower, and even more preferably 40 ° C. or lower. The smaller the collection temperature range, the less the fluctuation of the vapor deposition conditions, and the more likely it is that a homogeneous phase-separated structure is formed in the film thickness direction.
　分子量分画した含フッ素重合体は、要件（２）（３）を満たすならば、捕集温度幅の異なる複数の含フッ素重合体を混合してもよい。 The fluorinated polymer fractionated by molecular weight may be a mixture of a plurality of fluorinated polymers having different collection temperature ranges as long as the requirements (2) and (3) are satisfied.
（超臨界抽出）
　超臨界抽出は、超臨界流体の高い溶解性と拡散性を利用して抽出物を得る技術である。超臨界抽出では、例えば、超臨界流体として超臨界ＣＯ２を用い、超臨界ＣＯ２に相対的に低分子量の含フッ素重合体を溶解させ、抽出物として得ることができる。
　また、超臨界流体に対する添加剤（エントレーナー）として、含フッ素溶媒を用いることで、超臨界流体に対する含フッ素重合体の溶解性を高めることができる。 (Supercritical extraction)
Supercritical extraction is a technique for obtaining an extract by utilizing the high solubility and diffusivity of a supercritical fluid. In supercritical extraction, for example, supercritical CO 2 is used as a supercritical fluid, and a fluorine-containing polymer having a relatively low molecular weight is dissolved in the supercritical CO 2 to obtain an extract.
Further, by using a fluorine-containing solvent as an additive (entrainer) for the supercritical fluid, the solubility of the fluorine-containing polymer in the supercritical fluid can be enhanced.
　エントレーナーとして用いる含フッ素溶媒は、特に限定されない。例えば、下記方法で求める親フッ素パラメータＰＦが１以上である含フッ素溶媒が好ましい。（親フッ素パラメータＰＦ）
　３ｇのトルエンと３ｇのペルフルオロメチルシクロヘキサンとの二相系に、３０μＬの前記含フッ素溶媒を滴下してよく混合し一晩静置した後、前記トルエンに含まれる前記含フッ素溶媒と、前記ペルフルオロメチルシクロヘキサンに含まれる前記含フッ素溶媒とをガスクロマトグラフィーにより測定する。前記トルエン中の前記含フッ素溶媒の濃度（単位：ｍＬ／Ｌ）をＭＰ、前記ペルフルオロメチルシクロヘキサン中の前記含フッ素溶媒の濃度（単位：ｍＬ／Ｌ）をＭＦとしたとき、下記式（Ａ）で求められる値を親フッ素パラメータＰＦとする。
　ＰＦ＝ＭＦ／ＭＰ…（Ａ） The fluorine-containing solvent used as the entrainer is not particularly limited. For example, a fluorinated solvent is preferred Fluorophilic parameter P F calculated by the following method is one or more. (Parent fluorine parameter P F)
30 μL of the fluorine-containing solvent was added dropwise to a two-phase system of 3 g of toluene and 3 g of perfluoromethylcyclohexane, mixed well and allowed to stand overnight, and then the fluorine-containing solvent contained in the toluene and the perfluoromethyl were added. The fluorine-containing solvent contained in cyclohexane is measured by gas chromatography. The fluorinated solvent concentrations (unit: mL / L) of the toluene the M P, the concentration of the fluorinated solvent in the perfluoromethylcyclohexane (unit: mL / L) when the set to M F, the following equation ( the value obtained by a) a parent fluorine parameter P F.
P F = M F / M P ... (A)
　エントレーナーとして用いる含フッ素溶媒としては、例えば以下の化合物が挙げられる。
　１，１，１，２，２，３，３，４，４，５，５，６，６－トリデカフルオロヘキサン（ＡＣ－２０００、ＡＧＣ社製）（ＰＦ＝１２）
　１，１，１，２，２，３，３，４，４，５，５，６，６－トリデカフルオロオクタン（ＡＣ－６０００、ＡＧＣ社製）（ＰＦ＝５．６）
　サイトップ ＣＴ－ＳＯＬＶ１００Ｅ（ＡＧＣ社製）（ＰＦ＝８．２）
　サイトップ ＣＴ－ＳＯＬＶ１８０（ＡＧＣ社製）（ＰＦ＝∞）
　ＨＦＥ７３００（３Ｍ社製）（ＰＦ＝８．２）
　１，１，１，２，２，３，４，５，５，５－Ｄｅｃａｆｌｕｏｒｏｐｅｎｔａｎｅ（Ｖｅｒｔｒｅ　ＸＦ、Ｃｈｅｍｏｕｒｓ社製）（ＰＦ＝３．７）
　１Ｈ，１Ｈ，２Ｈ，２Ｈ－ペルフルオロオクタノール（ＰＦ＝１．１）
　１，１，２，２－テトラフルオロエチル－２，２，２－トリフルオロエチルエーテル（ＡＥ－３０００、ＡＧＣ社製）（ＰＦ＝０．６）
　ＨＣＦＣ－２２５ｃａ／ＨＣＦＣ－２２５ｃｂ（４５／５５）（ＰＦ＝０．３）
　ペルフルオロベンゼン（ＰＦ＝０．３）
　ヘキサフルオロ－２－プロパノール（ＰＦ＝０．２４）
　１Ｈ，１Ｈ，７Ｈ－ペルフルオロヘプタノール（ＰＦ＝０．２３）
　１Ｈ，１Ｈ，５Ｈ－ペルフルオロペンタノール（ＰＦ＝０．１） Examples of the fluorine-containing solvent used as an entrainer include the following compounds.
1,1,1,2,2,3,3,4,4,5,5,6,6- tridecafluoro-hexane (manufactured by AC-2000, AGC, Inc.) (P F = 12)
1,1,1,2,2,3,3,4,4,5,5,6,6- tridecafluoro-octane (manufactured by AC-6000, AGC, Inc.) (P F = 5.6)
Sai top CT-SOLV100E (manufactured by AGC, Inc.) (P F = 8.2)
Sai top CT-SOLV180 (manufactured by AGC, Inc.) (P F = ∞)
HFE7300 (3M Co., Ltd.) (P F = 8.2)
1,1,1,2,2,3,4,5,5,5-Decafluoropentane (Vertre XF, made Chemours, Inc.) (P F = 3.7)
1H, 1H, 2H, 2H- perfluoro-octanol (P F = 1.1)
1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether (manufactured by AE-3000, AGC, Inc.) (P F = 0.6)
HCFC-225ca / HCFC-225cb ( 45/55) (P F = 0.3)
Perfluorobenzene (P F = 0.3)
Hexafluoro-2-propanol (P F = 0.24)
1H, 1H, 7H- perfluoro heptanol (P F = 0.23)
1H, 1H, 5H- perfluoro-pentanol (P F = 0.1)
　抽出工程は、例えば超臨界ＣＯ２を用い、抽出圧力７．４ＭＰａ以上、抽出温度３１℃以上の条件で行うことができる。
　抽出圧力は、３０ＭＰａ以上が好ましく、５０ＭＰａ以上がより好ましく、７０ＭＰａ以上がさらに好ましい。抽出圧力の上限値には特に制限はないが、１００ＭＰａ以下が好ましい。抽出圧力の上限値と下限値とは、任意に組み合わせることができる。
　抽出温度は、４０℃以上が好ましく、８０℃以上がより好ましい。また、抽出温度は、３００℃以下が好ましく、２００℃以下がより好ましく、１００℃以下がさらに好ましい。抽出温度の上限値と下限値とは、任意に組み合わせることができる。
　上記範囲であれば、目的とする含フッ素重合体の分子量分画を効率よく行うことができる。 The extraction step can be carried out using, for example, supercritical CO 2 under the conditions of an extraction pressure of 7.4 MPa or more and an extraction temperature of 31 ° C. or more.
The extraction pressure is preferably 30 MPa or more, more preferably 50 MPa or more, and even more preferably 70 MPa or more. The upper limit of the extraction pressure is not particularly limited, but is preferably 100 MPa or less. The upper limit value and the lower limit value of the extraction pressure can be arbitrarily combined.
The extraction temperature is preferably 40 ° C. or higher, more preferably 80 ° C. or higher. The extraction temperature is preferably 300 ° C. or lower, more preferably 200 ° C. or lower, and even more preferably 100 ° C. or lower. The upper limit value and the lower limit value of the extraction temperature can be arbitrarily combined.
Within the above range, the molecular weight fractionation of the target fluorine-containing polymer can be efficiently performed.
（その他の要件）
　本実施形態の含フッ素重合体は、下記要件（４）（５）を満たすことが好ましい。
　要件（４）２５℃における貯蔵弾性率が１×１０７Ｐａ以上である。
　要件（５）降温速度２℃／分で含フッ素重合体を降温させたとき、貯蔵弾性率が１×１０６Ｐａ未満になる温度は１２０℃以上である。
　含フッ素重合体が上記要件（４）（５）を満たすと、含フッ素重合体の耐熱性が高くなる。 (Other requirements)
The fluorine-containing polymer of the present embodiment preferably satisfies the following requirements (4) and (5).
Requirement (4) a storage modulus at 25 ° C. is 1 × 10 7 Pa or higher.
Requirement (5) When the fluorine-containing polymer is cooled at a temperature lowering rate of 2 ° C./min, the temperature at which the storage elastic modulus is less than 1 × 10 6 Pa is 120 ° C. or higher.
When the fluorine-containing polymer satisfies the above requirements (4) and (5), the heat resistance of the fluorine-containing polymer becomes high.
　上記要件（４）（５）を満たす含フッ素重合体は、例えば含フッ素重合体が有するＰＰＶＥ単位の含有率を変更することで得られる。ＰＰＶＥ単位の含有率が増えると、貯蔵弾性率は低下する傾向にある。 The fluorine-containing polymer satisfying the above requirements (4) and (5) can be obtained, for example, by changing the content rate of the PPVE unit contained in the fluorine-containing polymer. As the content of PPVE units increases, the storage elastic modulus tends to decrease.
　本実施形態において、貯蔵弾性率は、動的粘弾性測定装置（例えば、アントンパール社製、ＭＣＲ５０２）、および粘弾性測定装置用加熱炉（例えば、アントンパール社製、ＣＴＤ４５０）を用いて測定する値を採用する。具体的には、試料（含フッ素重合体）を融点以上に加熱した後、定速降温モードで２℃／分で降温させる。上記測定装置を用い、歪み０．０１％、周波数１Ｈｚの条件で貯蔵弾性率（Ｇ’）を測定する。 In the present embodiment, the storage elastic modulus is measured using a dynamic viscoelasticity measuring device (for example, Anton Pearl Co., Ltd., MCR502) and a heating furnace for a viscoelasticity measuring device (for example, Anton Pearl Co., Ltd., CTD450). Adopt a value. Specifically, after heating the sample (fluorine-containing polymer) to a melting point or higher, the temperature is lowered at 2 ° C./min in the constant-speed temperature lowering mode. Using the above measuring device, the storage elastic modulus (G') is measured under the conditions of a strain of 0.01% and a frequency of 1 Hz.
　図２は、本実施形態の膜を示す概略断面図である。図２に示す膜１０は、有機半導体と含フッ素重合体の共蒸着膜であり、基板５０上に形成されている。
　膜１０においては、有機半導体と含フッ素重合体とが相分離しており、有機半導体のドメイン５１ｂと、上述した含フッ素重合体のドメイン５２ｂとを含む。ドメイン５１ｂとドメイン５２ｂとは膜厚方向に連続している。
　膜１０の面方向におけるドメイン５２ｂの大きさＤは、例えば１０ｎｍ～２０ｎｍ程度である。
　以下の説明では、膜１０が有する上述のような相分離構造を、ナノドメイン構造と称することがある。 FIG. 2 is a schematic cross-sectional view showing the film of the present embodiment. The film 10 shown in FIG. 2 is a co-deposited film of an organic semiconductor and a fluorine-containing polymer, and is formed on the substrate 50.
In the film 10, the organic semiconductor and the fluorine-containing polymer are phase-separated, and include the domain 51b of the organic semiconductor and the domain 52b of the fluorine-containing polymer described above. The domain 51b and the domain 52b are continuous in the film thickness direction.
The size D of the domain 52b in the plane direction of the film 10 is, for example, about 10 nm to 20 nm.
In the following description, the above-mentioned phase-separated structure of the membrane 10 may be referred to as a nanodomain structure.
　上述の通り、本実施形態で用いられる含フッ素重合体は、融点が２００℃以上であり、高い結晶性を有する。通常、高い結晶性を有する材料を用いて膜を形成した場合、耐熱性の高い膜が得られる。一方で、高い結晶性を有する材料を用いて形成した膜は、結晶化した部分が可視光を散乱するため、ヘイズが高く、透明性の低い膜となりやすい。このことから、高い結晶性を有する材料を用いて形成した膜は、透明性を必要とする光電子素子等への適用が難しかった。 As described above, the fluorine-containing polymer used in the present embodiment has a melting point of 200 ° C. or higher and has high crystallinity. Usually, when a film is formed using a material having high crystallinity, a film having high heat resistance can be obtained. On the other hand, a film formed by using a material having high crystallinity tends to have a high haze and low transparency because the crystallized portion scatters visible light. For this reason, it has been difficult to apply a film formed using a material having high crystallinity to a photoelectron device or the like that requires transparency.
　しかし、膜１０は、可視光に対して十分に小さいナノドメイン構造を有している。このような膜１０に含まれる含フッ素重合体の一部が結晶化したとしても、結晶化した部分の大きさは、ナノドメイン構造に収まる大きさとなる。
　そのため、膜１０は、可視光を散乱させにくく、高い透明性を示す。
　さらに、膜１０は、含フッ素重合体の高い結晶性に基づいて、高い耐熱性を有する。そのため、膜１０は、高温下に晒されてもナノドメイン構造が保持され、高い透明性を維持し得る。 However, the film 10 has a nanodomain structure that is sufficiently small with respect to visible light. Even if a part of the fluorine-containing polymer contained in such a film 10 is crystallized, the size of the crystallized part is a size that fits in the nanodomain structure.
Therefore, the film 10 is less likely to scatter visible light and exhibits high transparency.
Further, the film 10 has high heat resistance based on the high crystallinity of the fluorine-containing polymer. Therefore, the film 10 retains the nanodomain structure even when exposed to a high temperature, and can maintain high transparency.
　膜１０のヘイズおよびその耐熱性は、下記方法で測定することができる。
［ヘイズ測定用試料の作製］
　ガラス基板上に、α－ＮＰＤと、含フッ素重合体と、を共蒸着し、１００ｎｍの共蒸着膜を成膜して、ヘイズ測定用試料を得る。２つの材料の合計の蒸着速度は０．２ｎｍ／秒とする。蒸着速度を調整し、共蒸着膜におけるα－ＮＰＤと含フッ素重合体の体積比を所望の比率とする。 The haze of the film 10 and its heat resistance can be measured by the following method.
[Preparation of sample for haze measurement]
Α-NPD and a fluorine-containing polymer are co-deposited on a glass substrate to form a 100 nm co-deposited film to obtain a sample for haze measurement. The total deposition rate of the two materials is 0.2 nm / sec. The vapor deposition rate is adjusted so that the volume ratio of α-NPD to the fluorine-containing polymer in the co-deposited film is a desired ratio.
［ヘイズ測定］
　ヘイズ測定は、ヘイズメーター（東洋精機社製ヘイズガードＫ５０－２９０）を用いて行う。
　ヘイズ測定用試料の初期ヘイズを測定後、サンプル試料を１００℃に熱したホットプレート上で１時間加熱する。試料を常温に戻した後に、再度ヘイズを測定する。さらに、サンプル試料を１２０℃に熱したホットプレート上で１時間加熱し、同様にしてヘイズを測定する。 [Haze measurement]
Haze measurement is performed using a haze meter (Haze Guard K50-290 manufactured by Toyo Seiki Co., Ltd.).
After measuring the initial haze of the haze measurement sample, the sample sample is heated on a hot plate heated to 100 ° C. for 1 hour. After returning the sample to room temperature, measure the haze again. Further, the sample is heated on a hot plate heated to 120 ° C. for 1 hour, and the haze is measured in the same manner.
　得られたヘイズについて、以下のように評価する。
　〇：０．２未満、
　△：０．２以上０．５未満
　×：０．５以上 The obtained haze is evaluated as follows.
〇: Less than 0.2,
Δ: 0.2 or more and less than 0.5 ×: 0.5 or more
　膜１０を構成する含フッ素重合体と有機半導体との合計に対する含フッ素重合体の割合は、膜１０全体に対するドメイン５２ｂの体積と等しい。膜１０全体に対するドメイン５２ｂの割合は、２０～８０体積％が好ましい。含フッ素重合体の割合が２０体積％以上であると、含フッ素重合体を有さない有機半導体の膜と比べて、十分に低屈折率化された膜となる。また、含フッ素重合体の割合が８０体積％以下であると、膜１０の導電性を十分に確保できる。 The ratio of the fluorinated polymer to the total of the fluorinated polymer constituting the film 10 and the organic semiconductor is equal to the volume of the domain 52b with respect to the entire film 10. The ratio of the domain 52b to the entire membrane 10 is preferably 20 to 80% by volume. When the proportion of the fluorine-containing polymer is 20% by volume or more, the film has a sufficiently low refractive index as compared with the film of the organic semiconductor having no fluorine-containing polymer. Further, when the proportion of the fluorine-containing polymer is 80% by volume or less, the conductivity of the film 10 can be sufficiently ensured.
　膜１０の屈折率は、下記方法で作製した試料を用い、下記方法で測定することができる。
［屈折率測定用試料の作製］
　シリコン基板上に、α－ＮＰＤと、含フッ素重合体と、を共蒸着し、１００ｎｍの共蒸着膜を成膜して、屈折率測定用試料を得る。２つの材料の合計の蒸着速度は０．２ｎｍ／秒とする。蒸着速度を調整し、共蒸着膜におけるα－ＮＰＤと含フッ素重合体の体積比を所望の比率とする。
［屈折率測定］
　多入射角分光エリプソメトリー（例えば、ジェー・エー・ウーラム社製：Ｍ－２０００Ｕ）を用いて、シリコン基板上の膜に対して、光の入射角を４５～７５度の範囲で５度ずつ変えて測定を行う。それぞれの角度において、波長４５０～８００ｎｍの範囲で約１．６ｎｍおきにエリプソメトリーパラメータであるΨとΔを測定する。前記の測定データを用い、有機半導体の誘電関数をＣａｕｃｈｙモデルによりフィッティング解析を行い、波長６００ｎｍの光に対する蒸着膜の屈折率を得る。 The refractive index of the film 10 can be measured by the following method using a sample prepared by the following method.
[Preparation of sample for refractive index measurement]
Α-NPD and a fluorine-containing polymer are co-deposited on a silicon substrate to form a 100 nm co-deposited film to obtain a sample for refractive index measurement. The total deposition rate of the two materials is 0.2 nm / sec. The vapor deposition rate is adjusted so that the volume ratio of α-NPD to the fluorine-containing polymer in the co-deposited film is a desired ratio.
[Refractive index measurement]
Using multi-incident angle spectroscopic ellipsometry (eg, manufactured by JA Woolam: M-2000U), the incident angle of light is changed by 5 degrees in the range of 45 to 75 degrees with respect to the film on the silicon substrate. And measure. At each angle, ellipsometry parameters Ψ and Δ are measured at wavelengths in the range of 450-800 nm at intervals of approximately 1.6 nm. Using the above measurement data, the dielectric function of the organic semiconductor is subjected to fitting analysis by the Cauchy model to obtain the refractive index of the vapor-deposited film with respect to light having a wavelength of 600 nm.
　有機半導体は、公知のものを使用可能であり、本実施形態の膜１０を備える装置の機能に応じて、適切な材料を選択できる。
　例えば、有機半導体としては、有機ＥＬ素子の正孔注入層を構成する正孔注入材料、電子注入層を構成する電子注入材料、正孔輸送層を構成する正孔輸送材料、電子輸送層を構成する電子輸送材料、発光層を構成するホスト材料やゲスト材料を例示できる。 Known organic semiconductors can be used, and an appropriate material can be selected according to the function of the apparatus provided with the film 10 of the present embodiment.
For example, the organic semiconductor includes a hole injection material that constitutes a hole injection layer of an organic EL device, an electron injection material that constitutes an electron injection layer, a hole transport material that constitutes a hole transport layer, and an electron transport layer. Examples of electron transport materials, host materials and guest materials constituting the light emitting layer can be exemplified.
　正孔注入材料としては、芳香族アミン誘導体が好適に例示できる。具体例としては、下記のα－ＮＰＤ、ＴＡＰＣ、ＰＤＡ、ＴＰＤ、ｍ－ＭＴＤＡＴＡ等が挙げられるが、これらに限定されない。
Figure JPOXMLDOC01-appb-C000001
 As the hole injection material, an aromatic amine derivative can be preferably exemplified. Specific examples include, but are not limited to, the following α-NPD, TAPC, PDA, TPD, m-MTDATA, and the like.
Figure JPOXMLDOC01-appb-C000001
　前記以外の正孔注入材料としては、例えば、下記の、半導体材料、有機金属錯体材料、アリールアミン材料、高分子半導体材料等が挙げられる。また市販品としては下記のものが挙げられる。
　半導体材料：酸化モリブデン、酸化タングステン等の金属酸化物、フッ化アルミニウム、フッ化マグネシウム等の金属フッ化物
　有機金属錯体材料：銅フタロシアニン等
　アリールアミン材料：Ｎ，Ｎ’－ジフェニル－Ｎ，Ｎ’－ビス－［４－（フェニル－ｍ－トリル－アミノ）－フェニル］－ビフェニル－４，４’－ジアミン（ＤＮＴＰＤ）、Ｎ，Ｎ’－ジ（１－ナフチル）－Ｎ，Ｎ’－ジフェニルベンジジン（ＮＰＢ）、４，４’，４”－トリス（Ｎ，Ｎ－ジフェニルアミノ）トリフェニルアミン（ＴＤＡＴＡ）、ジピラジノ［２，３－ｆ：２’，３’－ｈ］キノキサリン－２，３，６，７，１０，１１－ヘキサカルボニトリル（ＨＡＴ－ＣＮ）、９，９’，９”－トリフェニル－９Ｈ，９’Ｈ，９”Ｈ－３，３’：６’，３”－テルカルバゾール（Ｔｒｉｓ－ＰＣｚ）、４，４’，４”－トリス（Ｎ，Ｎ－２－ナフチルフェニルアミノ）トリフェニルアミン（２－ＴＮＡＴＡ）等
　高分子半導体材料：ポリアニリン／ドデシルベンゼンスルホン酸（ＰＡＮＩ／ＤＢＳＡ）、ポリ（３，４－エチレンジオキシチオフェン）／ポリ（４－スチレンスルホネート）（ＰＥＤＯＴ／ＰＳＳ）、ポリアニリンカンファースルホン酸（ＰＡＮＩ／ＣＳＡ）、またはポリアニリン／ポリ（４－スチレンスルホネート）（ＰＡＮＩ／ＰＳＳ）等
　市販品：Ｎ－（ジフェニル－４－イル）－９，９－ジメチル－Ｎ－（４－（９－フェニル－９Ｈ－カルバゾイル－３イル）フェニル）－９Ｈ－フルオレン－２－アミン（以下、「ＨＴ２１１」という。）、ＨＴＭ０８１（Ｍｅｒｃｋ社製）、ＨＴＭ１６３（Ｍｅｒｃｋ社製）、ＨＴＭ２２２（Ｍｅｒｃｋ社製）、ＮＨＴ－５（ＮｏＶａｌｅｄ社製）、ＮＨＴ－１８（ＮｏＶａｌｅｄ社製）、ＮＨＴ－４９（ＮｏＶａｌｅｄ社製）、ＮＨＴ－５１（ＮｏＶａｌｅｄ社製）、ＮＤＰ－２（ＮｏＶａｌｅｄ社製）、ＮＤＰ－９（ＮｏＶａｌｅｄ社製）等 Examples of the hole injection material other than the above include the following semiconductor materials, organometallic complex materials, arylamine materials, polymer semiconductor materials, and the like. The following are examples of commercially available products.
Semiconductor materials: Metal oxides such as molybdenum oxide and tungsten oxide, metal fluorides such as aluminum fluoride and magnesium fluoride Organic metal complex materials: Copper phthalocyanines, etc. Aarylamine materials: N, N'-diphenyl-N, N'- Bis- [4- (phenyl-m-tolyl-amino) -phenyl] -biphenyl-4,4'-diamine (DNTPD), N, N'-di (1-naphthyl) -N, N'-diphenylbenzidine ( NPB), 4,4', 4 "-tris (N, N-diphenylamino) triphenylamine (TDATA), dipyrazino [2,3-f: 2', 3'-h] quinoxalin-2,3,6 , 7,10,11-Hexacarbonitrile (HAT-CN), 9,9', 9 "-triphenyl-9H, 9'H, 9"H-3,3':6', 3 "-tercarbazole (Tris-PCz), 4,4', 4 "-Tris (N, N-2-naphthylphenylamino) Triphenylamine (2-TNATA), etc. Polymer semiconductor materials: Polyaniline / dodecylbenzenesulfonic acid (PANI / DBSA) ), Poly (3,4-ethylenedioxythiophene) / Poly (4-styrenesulfonate) (PEDOT / PSS), Polyaniline camphorsulfonic acid (PANI / CSA), or Polyaniline / Poly (4-styrenesulfonate) (PANI / PSS) etc. Commercial products: N- (diphenyl-4-yl) -9,9-dimethyl-N- (4- (9-phenyl-9H-carbazoyl-3yl) phenyl) -9H-fluoren-2-amine ( Hereinafter referred to as "HT211"), HTM081 (manufactured by Merck), HTM163 (manufactured by Merck), HTM222 (manufactured by Merck), NHT-5 (manufactured by NoValed), NHT-18 (manufactured by NoValed), NHT- 49 (manufactured by NoValed), NHT-51 (manufactured by NoValed), NDP-2 (manufactured by NoValed), NDP-9 (manufactured by NoValed), etc.
　例示した正孔注入材料は、市販品を購入できる。これら正孔注入材料は、市販品を用いてもよいし合成品を用いてもよい。また、上記正孔注入材料は、単独で用いてもよく、２種以上を組み合わせて用いてもよい。 The hole injection material illustrated can be purchased commercially. As these hole injection materials, commercially available products or synthetic products may be used. Further, the hole injection material may be used alone or in combination of two or more.
　電子注入材料としては、公知のものを使用できる。具体例としては、ＬｉＦ，Ｃｓ２ＣＯ３，ＣｓＦ等の無機化合物や、下記のＡｌｑ３、ＰＢＤ、ＴＡＺ、ＢＮＤ、ＯＸＤ－７、８－ヒドロキシキノリノラト－リチウム（Ｌｉｑ）等が挙げられるが、これらに限定されない。他にも、ＮＤＮ－１（ＮｏＶａｌｅｄ社製）、ＮＤＮ－２６（ＮｏＶａｌｅｄ社製）等の市販品を使用できる。 As the electron injection material, a known material can be used. Specific examples include inorganic compounds such as LiF, Cs 2 CO 3 , CsF, and the following Alq 3 , PBD, TAZ, BND, OXD-7, 8-hydroxyquinolinolato-lithium (Liq), and the like. , Not limited to these. In addition, commercially available products such as NDN-1 (manufactured by NoValed) and NDN-26 (manufactured by NoValed) can be used.
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
　正孔輸送層の材料（正孔輸送材料）としては、例えば、前記正孔注入材料が挙げられるが、これらに限定されない。
　例えば、前記正孔注入材料として挙げたもの以外の、４，４’，４”－トリ（９－カルバゾイル）トリフェミルアミン（ＴＣＴＡ）、２，２’，７，７’－テトラキス（Ｎ，Ｎ－ジフェニルアミノ）－２，７－ジアミノ－９，９’－スピロビフルオレン（Ｓｐｉｒｏ－ＴＡＤ）、２，２’，７，７’－テトラキス（Ｎ，Ｎ－ジ－ｐ－メトキシフェニルアミノ）－９，９’－スピロビフルオレン（Ｓｐｉｒｏ－ＭｅＯＴＡＤ）等のアリールアミン材料を正孔輸送材料として使用できる。 Examples of the material of the hole transport layer (hole transport material) include, but are not limited to, the hole injection material.
For example, 4,4', 4 "-tri (9-carbazoyl) trifemilamine (TCTA), 2,2', 7,7'-tetrakis (N, N) other than those listed as the hole injection materials. -Diphenylamino) -2,7-diamino-9,9'-spirobifluorene (Spiro-TAD), 2,2', 7,7'-tetrakis (N, N-di-p-methoxyphenylamino)- Arylamine materials such as 9,9'-spirobifluorene (Spiro-MeOTAD) can be used as the hole transport material.
　前記正孔注入材料として挙げたもの以外の正孔輸送材料としては、トリアゾール誘導体、オキサジアゾール誘導体、イミダゾール誘導体、ピラゾリン誘導体、ピラゾロン誘導体、フェニレンジアミン誘導体、アリールアミン誘導体、アミノ置換カルコン誘導体、オキサゾール誘導体、スチリルアントラセン誘導体、フルオレノン誘導体、ヒドラゾン誘導体、スチルベン誘導体、シラザン誘導体等が挙げられる。なかでも、ポルフィリン化合物、芳香族第３級アミン化合物およびスチリルアミン化合物、特に芳香族第３級アミン化合物を用いることが好ましい。
　これら正孔輸送材料は、市販品を用いてもよいし合成品を用いてもよい。また、上記正孔輸送材料は、単独で用いてもよく、２種以上を組み合わせて用いてもよい。 Hole-transporting materials other than those listed as the hole-injecting materials include triazole derivatives, oxadiazole derivatives, imidazole derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, and oxazole derivatives. , Styrylanthracene derivative, fluorenone derivative, hydrazone derivative, stilben derivative, silazane derivative and the like. Among them, it is preferable to use a porphyrin compound, an aromatic tertiary amine compound and a styrylamine compound, particularly an aromatic tertiary amine compound.
As these hole transporting materials, commercially available products or synthetic products may be used. Further, the hole transporting material may be used alone or in combination of two or more.
　電子輸送層の材料（電子輸送材料）としては、公知のものを使用できる。例えば、電子輸送材料としては、前記電子注入材料が挙げられるが、これらに限定されない。前記電子注入材料として挙げたもの以外の電子輸送材料としては、２，２’，２''－（１，３，５－ベンジントリイル）－トリス（１－フェニル－１－Ｈ－ベンズイミダゾール）（ＴＰＢｉ）、２，９－ジメチル－４，７－ジフェニル－１，１０－フェナントロリン（ＢＣＰ）、２－（４－ｔｅｒｔ－ブチルフェニル）－５－（４－ビフェニリル）－１，３，４－オキサジアゾール（ｔ－Ｂｕ－ＰＢＤ）、シロール環を有するシロール誘導体が挙げられる。 As the material of the electron transport layer (electron transport material), a known material can be used. For example, the electron transport material includes, but is not limited to, the electron injection material. Examples of the electron transporting material other than those listed as the electron injecting material include 2,2', 2''-(1,3,5-benzinetriyl) -tris (1-phenyl-1-H-benzimidazole). (TPBi), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP), 2- (4-tert-butylphenyl) -5- (4-biphenylyl) -1,3,4- Examples thereof include oxadiazole (t-Bu-PBD) and a silol derivative having a silol ring.
　これら電子輸送材料は、市販品を用いてもよいし合成品を用いてもよい。また、上記電子輸送材料は、単独で用いてもよく、２種以上を組み合わせて用いてもよい。 As these electron transport materials, commercially available products or synthetic products may be used. Further, the electron transport material may be used alone or in combination of two or more.
　発光層の形成材料としては、蛍光材料、熱活性化遅延蛍光（ＴＡＤＦ）材料、りん光材料等、公知のものを採用できる。 As the material for forming the light emitting layer, known materials such as a fluorescent material, a thermal activated delayed fluorescence (TADF) material, and a phosphorescent material can be adopted.
　例えば、発光層の形成材料としては、（Ｅ）－２－（２－（４－（ジメチルアミノ）スチリル）－６－メチル－４Ｈ－ピラン－４－イリデン）マロノニトリル（ＤＣＭ）、４－（ジシアノメチレン）－２－メチル－６－ジュロリジル－９－エニル－４Ｈ－ピラン（ＤＣＭ２）、Ｒｕｂｒｅｎｅ、Ｃｏｕｍａｒｉｎ６、Ｉｒ（ｐｐｙ）３、（ｐｐｙ）２Ｉｒ（ａｃａｃ）等の発光ゲスト材料、４，４’－ビス（９Ｈ－カルバゾール－９－イル）ビフェニル（ＣＢＰ）、３,３'－ジ(９Ｈ－カルバゾール－９－イル)－１,１'－ビフェニル（ｍＣＢＰ）等のりん光ホスト材料、ＡＤＮ、Ａｌｑ３等の蛍光ホスト材料、ポリフェニレンビニレン（ＰＰＶ）、ＭＥＨ－ＰＰＶ等のポリマー材料が挙げられるが、これらに限定されない。 For example, examples of the material for forming the light emitting layer include (E) -2- (2- (4- (dimethylamino) styryl) -6-methyl-4H-pyran-4-iriden) malononitrile (DCM) and 4- (dicyano). Luminescent guest materials such as methylene) -2-methyl-6-juloridyl-9-enyl-4H-pyran (DCM 2 ), rubrene, polymer6, Ir (ppy) 3 , (ppy) 2 Ir (acac), 4, 4 Phosphorescent host material such as'-bis (9H-carbazole-9-yl) biphenyl (CBP), 3,3'-di (9H-carbazole-9-yl) -1,1'-biphenyl (mCBP), ADN , Fluorescent host materials such as Alq3, and polymer materials such as polyphenylene vinylene (PPV) and MEH-PPV, but are not limited thereto.
　発光層の形成材料は、単独で用いてもよく、２種以上を組み合わせて用いてもよい。発光層の形成材料は、所望の発光波長に応じて適宜選択される。 The material for forming the light emitting layer may be used alone or in combination of two or more. The material for forming the light emitting layer is appropriately selected according to the desired emission wavelength.
　膜１０の形成材料である有機半導体は、分子量が３００～１０００であることが好ましい。有機半導体の分子量は、４００以上であることがより好ましい。また、有機半導体の分子量は９００以下であることがより好ましい。
　上記有機半導体の分子量が３００以上であれば、有機半導体のガラス転移点（Ｔｇ）が高くなり、有機半導体膜の耐熱性が向上する。分子量が１０００以下であれば、有機半導体の蒸気圧が高くなり、熱分解温度以下で蒸着することが可能となる。
　有機半導体の分子量の上限値と下限値とは、任意に組み合わせることができる。すなわち、有機半導体の分子量は、３００～９００であってもよく、４００～１０００であってもよく、４００～９００であってもよい。
　有機半導体の分子量は、ＴＯＦ－ＳＩＭＳ（Ｔｉｍｅ－ｏｆ－Ｆｌｉｇｈｔ　Ｓｅｃｏｎｄａｒｙ　Ｉｏｎ　Ｍａｓｓ　Ｓｐｅｃｔｒｏｍｅｔｒｙ）を用いた測定で求めることができる。 The organic semiconductor that is the material for forming the film 10 preferably has a molecular weight of 300 to 1000. The molecular weight of the organic semiconductor is more preferably 400 or more. Further, the molecular weight of the organic semiconductor is more preferably 900 or less.
When the molecular weight of the organic semiconductor is 300 or more, the glass transition point (Tg) of the organic semiconductor becomes high, and the heat resistance of the organic semiconductor film is improved. When the molecular weight is 1000 or less, the vapor pressure of the organic semiconductor becomes high, and the vapor deposition can be performed at the thermal decomposition temperature or less.
The upper limit value and the lower limit value of the molecular weight of the organic semiconductor can be arbitrarily combined. That is, the molecular weight of the organic semiconductor may be 300 to 900, 400 to 1000, or 400 to 900.
The molecular weight of the organic semiconductor can be determined by measurement using TOF-SIMS (Time-of-Flight Second Method Ion Mass Spectrometry).
　また、膜１０は、ドーパントをさらに含んでいてもよい。ドーパントは、公知のものを使用可能であり、本実施形態の膜１０を備える装置の機能に応じて、適切な材料を選択できる。ドーパントを含むことにより、膜１０は導電性を高めることができる。
　例えば、正孔注入材料として用いられるドーパントとしては、ＴＣＮＱ、Ｆ４－ＴＣＮＱ、ＰＰＤＮ、ＴＣＮＮＱ、Ｆ６－ＴＣＮＮＱ、ＨＡＴ－ＣＮ、ＨＡＴＮＡ、ＨＡＴＮＡ－Ｃｌ６、ＨＡＴＮＡ－Ｆ６、Ｃ６０Ｆ３６、Ｆ１６－ＣｕＰｃ、ＮＤＰ－２（Ｎｏｖａｌｅｄ社製）、ＮＤＰ－９（Ｎｏｖａｌｅｄ社製）等の有機ドーパントやＭｏＯ３、Ｖ２Ｏ５、ＷＯ３、ＲｅＯ３、ＣｕＩ等の無機ドーパントが挙げられる。
　電子注入材料として用いられるドーパントとしては、８－ヒドロキシキノリノラト－リチウム（Ｌｉｑ）、ＮＤＮ－１（Ｎｏｖａｌｅｄ社製）、ＮＤＮ－２６（Ｎｏｖａｌｅｄ社製）等が挙げられる。 Further, the film 10 may further contain a dopant. As the dopant, a known one can be used, and an appropriate material can be selected according to the function of the apparatus provided with the film 10 of the present embodiment. By including the dopant, the film 10 can be made more conductive.
For example, as the dopant used as a hole injection material, TCNQ, F 4 -TCNQ, PPDN , TCNNQ, F 6 -TCNNQ, HAT-CN, HATNA, HATNA-Cl 6, HATNA-F 6, C 60 F 36, F 16 -CuPc, NDP-2 ( Novaled Co.) include NDP-9 (Novaled Co.) organic dopant and MoO 3 etc., V 2 O 5, WO 3 , ReO 3, of CuI and inorganic dopants.
Examples of the dopant used as the electron injection material include 8-hydroxyquinolinolato-lithium (Liq), NDN-1 (manufactured by Novaled), NDN-26 (manufactured by Novaled) and the like.
　図３～５は、上述した膜１０を製造する工程を示す模式図である。
　まず、図３に示すように、膜１０を形成する基板５０を用意する。このような基板５０を真空蒸着装置のチャンバー５００内に設置し、有機半導体の蒸着源（るつぼ）５１と含フッ素重合体の蒸着源（るつぼ）５２とから、有機半導体５１ａ、含フッ素重合体５２ａを供給して共蒸着する。なお、図３では、有機半導体と含フッ素重合体とを別々の蒸着源から蒸着させることとして示しているが、同一の蒸着源から蒸着させることとしてもよい。 3 to 5 are schematic views showing a process of manufacturing the above-mentioned film 10.
First, as shown in FIG. 3, a substrate 50 on which the film 10 is formed is prepared. Such a substrate 50 is installed in the chamber 500 of the vacuum vapor deposition apparatus, and the organic semiconductor 51a and the fluorine-containing polymer 52a are provided from the organic semiconductor vapor deposition source (rutsubo) 51 and the fluorine-containing polymer vapor deposition source (rutsubo) 52. Is supplied and co-deposited. Although FIG. 3 shows that the organic semiconductor and the fluorine-containing polymer are vapor-deposited from different vapor deposition sources, they may be vapor-deposited from the same vapor deposition source.
　有機半導体５１ａ、含フッ素重合体５２ａとしては、上述の膜１０を構成する有機半導体、含フッ素重合体をそれぞれ用いることができる。
　共蒸着時には、基板５０上に形成される共蒸着膜において、含フッ素重合体と有機半導体の合計に対する含フッ素重合体の比率が２０～８０体積％となるように、蒸着条件を設定する。 As the organic semiconductor 51a and the fluorine-containing polymer 52a, the organic semiconductor and the fluorine-containing polymer constituting the above-mentioned film 10 can be used, respectively.
At the time of co-evaporation, the vapor deposition conditions are set so that the ratio of the fluorine-containing polymer to the total of the fluorine-containing polymer and the organic semiconductor is 20 to 80% by volume in the co-deposited film formed on the substrate 50.
　有機半導体５１ａは、蒸着時の加熱で分解しないものが好ましい。蒸着時の加熱で分解しないことは、用いる有機半導体について、下記方法で重量減少率を求めることで判断できる。 The organic semiconductor 51a is preferably one that does not decompose by heating during vapor deposition. The fact that the organic semiconductor is not decomposed by heating during vapor deposition can be determined by determining the weight reduction rate of the organic semiconductor to be used by the following method.
（判断方法）
　真空示差熱天秤（アドバンス理工社製：ＶＰＥ－９０００）を用いて測定する。有機半導体５０ｍｇを内径７ｍｍのセルに仕込み、１×１０－３Ｐａ～１×１０－４Ｐａの真空度にて、毎分２℃で５００℃まで昇温した際の有機半導体の重量減少率（％）を測定し、重量減少率が５０％となる温度（Ｔｄ５０）を求める。
　次いで、熱重量示差熱分析装置（日立ハイテクサイエンス社製：ＳＴＡ７２００）を用いて、窒素フロー下において、毎分１０℃で４５０℃まで昇温した際の有機半導体の重量減少率を測定し、Ｔｄ５０における重量減少率を求める。 (Judgment method)
Measure using a vacuum differential thermal balance (manufactured by Advance Riko Co., Ltd .: VPE-9000). The weight reduction rate of the organic semiconductor when 50 mg of the organic semiconductor is charged into a cell having an inner diameter of 7 mm and the temperature is raised to 500 ° C. at 2 ° C. per minute at a vacuum degree of 1 × 10 -3 Pa to 1 × 10 -4 Pa ( %) Is measured, and the temperature (T d50 ) at which the weight loss rate becomes 50% is determined.
Next, using a thermogravimetric differential thermal analyzer (manufactured by Hitachi High-Tech Science Co., Ltd .: STA7200), the weight loss rate of the organic semiconductor when the temperature was raised to 450 ° C. at 10 ° C. per minute under a nitrogen flow was measured, and T. The weight loss rate at d50 is calculated.
　Ｔｄ５０における常圧での重量減少率が１％以下であれば、減圧下のＴｄ５０において重量減少した理由が熱分解ではなく、昇華によるものであると判断する。このような有機半導体は、蒸着時の加熱で分解しない、すなわち蒸着に適した材料であると判断できる。
　一方で、Ｔｄ５０における常圧での重量減少率が１％を超える場合、減圧下のＴｄ５０において重量減少した理由が熱分解であると判断する。このような有機半導体は、蒸着時の加熱で分解するため、蒸着に不適であると判断できる。 If the weight loss rate at normal pressure at T d50 is 1% or less, it is determined that the reason for the weight loss at T d50 under reduced pressure is not thermal decomposition but sublimation. It can be determined that such an organic semiconductor does not decompose by heating during vapor deposition, that is, it is a material suitable for vapor deposition.
On the other hand, when the weight loss rate at normal pressure at T d50 exceeds 1%, it is determined that the reason for the weight loss at T d50 under reduced pressure is thermal decomposition. Since such an organic semiconductor is decomposed by heating during vapor deposition, it can be judged that it is not suitable for vapor deposition.
　図４に示すように、有機半導体と含フッ素重合体とを共蒸着すると、基板上では、有機半導体と含フッ素重合体とが相分離し、有機半導体のドメイン５１ｂと、含フッ素重合体のドメイン５２ｂとが形成されると考えられる。
　含フッ素重合体のドメイン５２ｂの大きさ（直径）は、共蒸着を行う基板５０の表面エネルギーと、含フッ素重合体の表面エネルギーとの関係によって、少ないバラツキで一定の数値範囲に収まるものと考えられる。すなわち、用いる含フッ素重合体が基板５０の表面に塗れ広がりやすい場合には、ドメイン５２ｂは大きく広がりやすいと考えられ、含フッ素重合体が基板５０の表面に塗れ広がりにくい場合には、ドメイン５２ｂの直径は小さくなりやすいと考えられる。 As shown in FIG. 4, when the organic semiconductor and the fluorine-containing polymer are co-deposited, the organic semiconductor and the fluorine-containing polymer are phase-separated on the substrate, and the domain 51b of the organic semiconductor and the domain of the fluorine-containing polymer are separated. It is considered that 52b and 52b are formed.
It is considered that the size (diameter) of the domain 52b of the fluorine-containing polymer falls within a certain numerical range with a small variation depending on the relationship between the surface energy of the substrate 50 to be co-deposited and the surface energy of the fluorine-containing polymer. Be done. That is, when the fluorine-containing polymer used is easily spread on the surface of the substrate 50, the domain 52b is considered to be large and easily spread, and when the fluorine-containing polymer is difficult to spread on the surface of the substrate 50, the domain 52b is spread. It is thought that the diameter tends to be small.
　図５に示すように、共蒸着を継続すると、蒸着源５１から昇華した有機半導体５１ａは、ドメイン５２ｂに堆積するよりもエネルギー的に安定であるため、有機半導体のドメイン５１ｂに堆積すると考えられる。同様に、蒸着源５２から昇華した含フッ素重合体５２ａは、ドメイン５１ｂに堆積するよりもエネルギー的に安定であるため、含フッ素重合体のドメイン５２ｂに堆積すると考えられる。
　これにより、共蒸着膜の膜厚方向に連続した有機半導体のドメイン５１ｂと、共蒸着膜の膜厚方向に連続した含フッ素重合体のドメイン５２ｂとが形成される。また、基板５０の法線方向から共蒸着膜を見た場合、ドメイン５２ｂの直径は、共蒸着膜の膜厚方向で大きく変化することなく、基板５０表面に形成される最初のドメイン５２ｂの大きさを反映したものとなる。
　このとき、上述の含フッ素重合体を用いることにより、ドメイン５２ｂを構成する含フッ素重合体は分子量が狭く、蒸着の初期と終期とで物性の差が小さくなる。そのため、得られる膜１０の品質が安定しやすい。 As shown in FIG. 5, when the co-evaporation is continued, the organic semiconductor 51a sublimated from the vapor deposition source 51 is energetically more stable than the deposition in the domain 52b, so that it is considered that the organic semiconductor 51a is deposited in the domain 51b of the organic semiconductor. Similarly, since the fluorine-containing polymer 52a sublimated from the vapor deposition source 52 is more energetically stable than depositing in the domain 51b, it is considered that the fluorine-containing polymer 52a is deposited in the domain 52b of the fluorine-containing polymer.
As a result, the domain 51b of the organic semiconductor continuous in the film thickness direction of the co-deposited film and the domain 52b of the fluorine-containing polymer continuous in the film thickness direction of the co-deposited film are formed. Further, when the co-deposited film is viewed from the normal direction of the substrate 50, the diameter of the domain 52b does not change significantly in the film thickness direction of the co-deposited film, and is the size of the first domain 52b formed on the surface of the substrate 50. It will reflect the above.
At this time, by using the above-mentioned fluorine-containing polymer, the fluorine-containing polymer constituting the domain 52b has a narrow molecular weight, and the difference in physical properties between the initial stage and the final stage of vapor deposition becomes small. Therefore, the quality of the obtained film 10 is likely to be stable.
　上記のようにして、膜１０を製造する。
　ここで、膜１０を加熱した場合には、ドメイン５２ｂが加熱により移動しやすくなり、近接するドメイン５２ｂ同士が合一して、膜１０のナノドメイン構造が崩れることがある。これに対し、用いる含フッ素重合体が上述の要件（４）（５）を満たしていると、ドメイン５２ｂが合一し難く、ナノドメイン構造を維持しやすい膜１０となる。 The film 10 is manufactured as described above.
Here, when the film 10 is heated, the domains 52b are easily moved by the heating, and the adjacent domains 52b may coalesce and the nanodomain structure of the film 10 may be destroyed. On the other hand, when the fluorine-containing polymer used satisfies the above-mentioned requirements (4) and (5), the domain 52b is difficult to unite, and the film 10 easily maintains the nanodomain structure.
　以上のような構成の含フッ素重合体によれば、耐熱性が高く、蒸着に適した含フッ素重合体を提供できる。
　また、以上のような構成の膜によれば、低屈折率化され、高透明かつ高耐熱性であり、品質の安定した膜となる。
　また、以上のような構成の膜の製造方法によれば、このような膜を容易に製造できる。
　なお、本実施形態においては、本実施形態の含フッ素重合体と有機半導体とを共蒸着して膜１０を形成したが、これに限らない。本実施形態の含フッ素重合体と有機半導体とを含む膜は、塗布などのウェットプロセスによって製造してもよい。 According to the fluorine-containing polymer having the above-mentioned structure, it is possible to provide a fluorine-containing polymer having high heat resistance and suitable for vapor deposition.
Further, according to the film having the above-mentioned structure, the film has a low refractive index, high transparency, high heat resistance, and stable quality.
Further, according to the method for producing a film having the above-mentioned structure, such a film can be easily produced.
In the present embodiment, the fluorine-containing polymer of the present embodiment and the organic semiconductor are co-deposited to form the film 10, but the present invention is not limited to this. The film containing the fluorine-containing polymer and the organic semiconductor of the present embodiment may be produced by a wet process such as coating.
［第２実施形態］
　図６は、本発明の第２実施形態に係る有機光電子素子（有機ＥＬ素子）１００を示す断面模式図である。有機ＥＬ素子１００は、基板１１０、陽極１１１、正孔注入層１１２、正孔輸送層１１３、発光層１１４、電子輸送層１１５、電子注入層１１６、陰極１１７がこの順に積層した構造を有している。本実施形態の有機ＥＬ素子１００は、発光層１１４で生じた光Ｌが、陰極１１７を介して外部へ射出されるトップエミッション方式を採用している。 [Second Embodiment]
FIG. 6 is a schematic cross-sectional view showing an organic photoelectronic device (organic EL device) 100 according to a second embodiment of the present invention. The organic EL element 100 has a structure in which a substrate 110, an anode 111, a hole injection layer 112, a hole transport layer 113, a light emitting layer 114, an electron transport layer 115, an electron injection layer 116, and a cathode 117 are laminated in this order. There is. The organic EL element 100 of the present embodiment employs a top emission method in which the light L generated in the light emitting layer 114 is emitted to the outside via the cathode 117.
（基板）
　基板１１０は、光透過性を備えていてもよく、光透過性を備えなくてもよい。基板１１０の形成材料としては、ガラス、石英ガラス、窒化ケイ素等の無機物や、ポリイミド樹脂、アクリル樹脂、ポリカーボネート樹脂等の有機高分子（樹脂）を用いることができる。また、表面の絶縁性が確保されるならば、基板１１０の形成材料として金属材料を採用することもできる。
　また、基板１１０は、有機ＥＬ素子に電気的に接続される不図示の各種配線、駆動素子を備えている。 (substrate)
The substrate 110 may or may not have light transmission. As the material for forming the substrate 110, an inorganic substance such as glass, quartz glass, or silicon nitride, or an organic polymer (resin) such as a polyimide resin, an acrylic resin, or a polycarbonate resin can be used. Further, if the insulating property of the surface is ensured, a metal material can be adopted as a material for forming the substrate 110.
Further, the substrate 110 includes various wirings and driving elements (not shown) that are electrically connected to the organic EL element.
（陽極）
　陽極１１１は、基板１１０上に形成され、正孔輸送層１１３に正孔（ホール）を供給する。また、陽極１１１は、発光層１１４から発せられた光を反射する光反射性を有する。 (anode)
The anode 111 is formed on the substrate 110 and supplies holes to the hole transport layer 113. Further, the anode 111 has a light reflectivity that reflects the light emitted from the light emitting layer 114.
　陽極１１１の形成材料としては、ＩＴＯ（Ｉｎｄｉｕｍ　Ｔｉｎ　Ｏｘｉｄｅ：インジウムドープ酸化錫）やＩＺＯ（Ｉｎｄｉｕｍ　Ｚｉｎｃ　Ｏｘｉｄｅ:インジウムドープ酸化亜鉛）等の導電性金属酸化物を用いることができる。また、陽極１１１に光反射性を付与するため、陽極１１１の基板１１０側には、金属材料を形成材料とする反射膜が設けられている。すなわち、陽極１１１は、導電性金属酸化物を形成材料とする層と、反射膜との積層構造を有する。
　また、陽極１１１の形成材料として、銀を用いることとしてもよい。 As a material for forming the anode 111, a conductive metal oxide such as ITO (Indium Tin Oxide: indium-doped tin oxide) or IZO (Indium Zinc Oxide: indium-doped zinc oxide) can be used. Further, in order to impart light reflectivity to the anode 111, a reflective film made of a metal material is provided on the substrate 110 side of the anode 111. That is, the anode 111 has a laminated structure of a layer made of a conductive metal oxide as a forming material and a reflective film.
Further, silver may be used as a material for forming the anode 111.
　陽極１１１の厚さは、特に制限されないが、３０～３００ｎｍが好ましい。陽極１１１の厚さは、例えば１００ｎｍである。 The thickness of the anode 111 is not particularly limited, but is preferably 30 to 300 nm. The thickness of the anode 111 is, for example, 100 nm.
（正孔注入層）
　正孔注入層１１２は、陽極１１１と正孔輸送層１１３との間に形成されている。正孔注入層１１２は、陽極１１１から正孔輸送層１１３への正孔の注入を容易にする機能を有する。なお、正孔注入層１１２は形成しなくてもよい。
　正孔注入層１１２は、上述した正孔注入材料を用いて形成できる。
　正孔注入層１１２の厚さは、特に制限されないが、１～１００ｎｍが好ましい。正孔注入層１１２の厚さは、例えば５ｎｍである。 (Hole injection layer)
The hole injection layer 112 is formed between the anode 111 and the hole transport layer 113. The hole injection layer 112 has a function of facilitating the injection of holes from the anode 111 into the hole transport layer 113. The hole injection layer 112 does not have to be formed.
The hole injection layer 112 can be formed by using the hole injection material described above.
The thickness of the hole injection layer 112 is not particularly limited, but is preferably 1 to 100 nm. The thickness of the hole injection layer 112 is, for example, 5 nm.
（正孔輸送層）
　正孔輸送層１１３は、正孔注入層１１２上に形成されている。正孔輸送層１１３は、陽極１１１から注入された正孔を発光層１１４に向けて良好に輸送する機能を有する。
　正孔輸送層１１３は、上述した正孔輸送材料を用いて形成できる。
　正孔輸送層１１３は、単層であってもよく、正孔輸送材料の層が複数積層した構成であってもよい。正孔輸送層１１３が正孔輸送材料の層が複数積層した積層体である場合、各層を構成する正孔輸送材料は、同じであってもよく、互いに異なっていてもよい。 (Hole transport layer)
The hole transport layer 113 is formed on the hole injection layer 112. The hole transport layer 113 has a function of satisfactorily transporting the holes injected from the anode 111 toward the light emitting layer 114.
The hole transport layer 113 can be formed by using the hole transport material described above.
The hole transport layer 113 may be a single layer, or may have a configuration in which a plurality of layers of hole transport materials are laminated. When the hole transport layer 113 is a laminated body in which a plurality of layers of hole transport materials are laminated, the hole transport materials constituting each layer may be the same or different from each other.
　正孔輸送層１１３は、波長域４５０～８００ｎｍにおける吸収係数が５０００ｃｍ－１以下であることが好ましく、１０００ｃｍ－１以下であることがより好ましく、上記波長域において吸収帯を有さないことが特に好ましい。
　正孔輸送層１１３を構成する各層の吸収係数が５０００ｃｍ－１を超える場合、光が厚み１００ｎｍの正孔輸送層を１回通過すると通過前の光の全量を１００％としたときに対し５％の光が吸収される。有機ＥＬ素子の内部では光の多重干渉により、正孔輸送層１１３を通過するときの光の吸収による損失が累積する。そのため、正孔輸送層を通過する際における光吸収が光取出し効率を大きく低減させる要因となる。光吸収が十分小さい正孔輸送層を用いることは、有機ＥＬ素子の発光効率を損なわないために極めて重要である。有機ＥＬ素子の発光効率が損なわれないことによりエネルギー利用効率が高くなり、かつ、光吸収に基づく発熱が抑制される結果として素子寿命が長くなる。 Hole transport layer 113 is preferably an absorption coefficient in the wavelength range 450 ~ 800 nm is 5000 cm -1 or less, more preferably 1000 cm -1 or less, to have no absorption band in the wavelength region in particular preferable.
When the absorption coefficient of each layer constituting the hole transport layer 113 exceeds 5000 cm-1 , once the light passes through the hole transport layer having a thickness of 100 nm, it is 5% compared to the case where the total amount of light before passing is 100%. Light is absorbed. Inside the organic EL element, the loss due to the absorption of light when passing through the hole transport layer 113 is accumulated due to the multiple interference of light. Therefore, light absorption when passing through the hole transport layer becomes a factor that greatly reduces the light extraction efficiency. It is extremely important to use a hole transport layer having sufficiently small light absorption so as not to impair the luminous efficiency of the organic EL device. Since the luminous efficiency of the organic EL element is not impaired, the energy utilization efficiency is increased, and as a result of suppressing heat generation due to light absorption, the device life is extended.
　正孔輸送層１１３の厚さは特に制限されないが、１０～２５０ｎｍが好ましく、２０～１５０ｎｍがより好ましい。 The thickness of the hole transport layer 113 is not particularly limited, but is preferably 10 to 250 nm, more preferably 20 to 150 nm.
（発光層）
　発光層１１４は、正孔輸送層１１３の上に形成されている。発光層１１４では、陽極１１１から注入された正孔および陰極１１７から注入された電子が再結合し、光子を放出して発光する。その際の発光波長は、発光層１１４の形成材料に応じて定まる。発光層１１４は、本発明における「活性層」に該当する。
　発光層１１４は、上述した発光層の形成材料を用いて形成できる。
　発光層の形成材料は、単独で用いてもよく、２種以上を組み合わせて用いてもよく、所望の発光波長に応じて適宜選択される。
　発光層１１４の厚さは、特に制限されないが、１０～３０ｎｍが好ましい。発光層１１４の厚さは、例えば１５ｎｍである。 (Light emitting layer)
The light emitting layer 114 is formed on the hole transport layer 113. In the light emitting layer 114, the holes injected from the anode 111 and the electrons injected from the cathode 117 are recombined to emit photons to emit light. The emission wavelength at that time is determined according to the material for forming the light emitting layer 114. The light emitting layer 114 corresponds to the "active layer" in the present invention.
The light emitting layer 114 can be formed by using the above-mentioned material for forming the light emitting layer.
The material for forming the light emitting layer may be used alone or in combination of two or more, and is appropriately selected according to a desired emission wavelength.
The thickness of the light emitting layer 114 is not particularly limited, but is preferably 10 to 30 nm. The thickness of the light emitting layer 114 is, for example, 15 nm.
（電子輸送層）
　電子輸送層１１５は、発光層１１４の上に形成されている。電子輸送層１１５は、陰極１１７から注入された電子を発光層１１４に向けて良好に輸送する機能を有する。
　電子輸送層１１５は、上述した電子輸送材料を用いて形成できる。
　電子輸送層１１５の厚さは、特に制限されないが、３０～８０ｎｍが好ましい。電子輸送層１１５の厚さは、例えば６０ｎｍである。 (Electronic transport layer)
The electron transport layer 115 is formed on the light emitting layer 114. The electron transport layer 115 has a function of satisfactorily transporting the electrons injected from the cathode 117 toward the light emitting layer 114.
The electron transport layer 115 can be formed by using the electron transport material described above.
The thickness of the electron transport layer 115 is not particularly limited, but is preferably 30 to 80 nm. The thickness of the electron transport layer 115 is, for example, 60 nm.
（電子注入層）
　電子注入層１１６は、陰極１１７と電子輸送層１１５との間に設けられている。電子注入層１１６は、陰極１１７から電子輸送層１１５への電子の注入を容易にする機能を有する。電子注入層１１６の形成材料としては、上述した電子注入材料を使用できる。
　なお、電子注入層１１６は形成しなくてもよい。
　電子注入層１１６の厚さは、特に制限されないが、０．５～２ｎｍが好ましい。電子注入層１１６の厚さは、例えば１ｎｍである。 (Electron injection layer)
The electron injection layer 116 is provided between the cathode 117 and the electron transport layer 115. The electron injection layer 116 has a function of facilitating the injection of electrons from the cathode 117 into the electron transport layer 115. As the material for forming the electron injection layer 116, the above-mentioned electron injection material can be used.
The electron injection layer 116 does not have to be formed.
The thickness of the electron injection layer 116 is not particularly limited, but is preferably 0.5 to 2 nm. The thickness of the electron injection layer 116 is, for example, 1 nm.
（陰極）
　陰極１１７は、電子注入層１１６の上に形成されている。陰極１１７は、電子注入層１１６に電子を注入する機能を有する。陰極１１７の形成材料としては、公知のものを採用できる。例えば、陰極１１７の形成材料として、ＭｇＡｇ電極、Ａｌ電極が挙げられる。陰極１１７の表面にはＬｉＦ等のバッファー層が形成されていてもよい。
　陰極１１７は、全体として発光層１１４から発せられた光の一部を反射し、残部を透過する程度に薄く形成された半透過膜である。
　陰極１１７の厚さは、特に制限されないが、５～３０ｎｍが好ましい。陰極１１７の厚さは、例えば５ｎｍである。 (cathode)
The cathode 117 is formed on the electron injection layer 116. The cathode 117 has a function of injecting electrons into the electron injection layer 116. As a material for forming the cathode 117, a known material can be adopted. For example, examples of the material for forming the cathode 117 include an MgAg electrode and an Al electrode. A buffer layer such as LiF may be formed on the surface of the cathode 117.
The cathode 117 is a semi-transmissive film formed thin enough to reflect a part of the light emitted from the light emitting layer 114 as a whole and pass through the rest.
The thickness of the cathode 117 is not particularly limited, but is preferably 5 to 30 nm. The thickness of the cathode 117 is, for example, 5 nm.
（マイクロキャビティ構造）
　本実施形態の有機ＥＬ素子１００においては、陽極１１１と陰極１１７が、陽極１１１と陰極１１７との間で光を共振させる光共振構造（マイクロキャビティ）を構成している。陽極１１１と陰極１１７との間では、発光層１１４で生じた光が反射を繰り返し、陽極１１１と陰極１１７との間の光路長と合致した波長の光が共振して増幅される。一方で、陽極１１１と陰極１１７との間の光路長と合致しない波長の光は減衰する。
　ここでいう「光路長」は、素子外部に射出される所望の光の波長と、当該所望の光の波長における各層の屈折率と、を用いて算出されるものとする。 (Microcavity structure)
In the organic EL element 100 of the present embodiment, the anode 111 and the cathode 117 form an optical resonance structure (microcavity) in which light is resonated between the anode 111 and the cathode 117. The light generated by the light emitting layer 114 is repeatedly reflected between the anode 111 and the cathode 117, and the light having a wavelength matching the optical path length between the anode 111 and the cathode 117 is resonated and amplified. On the other hand, light having a wavelength that does not match the optical path length between the anode 111 and the cathode 117 is attenuated.
The "optical path length" referred to here is calculated using the wavelength of the desired light emitted to the outside of the device and the refractive index of each layer at the desired wavelength of the light.
　陽極１１１と陰極１１７との間の光路長は、例えば発光層１１４で生じる光Ｌの中心波長の整数倍に設定されている。この場合、発光層１１４で発せられた光Ｌは、中心波長に近いほど増幅され、中心波長から離れるほど減衰して有機ＥＬ素子１００の外部に射出される。このようにして、有機ＥＬ素子１００から射出される光Ｌは、発光スペクトルの半値幅が狭く、色純度が向上したものとなる。 The optical path length between the anode 111 and the cathode 117 is set to, for example, an integral multiple of the center wavelength of the light L generated in the light emitting layer 114. In this case, the light L emitted by the light emitting layer 114 is amplified as it is closer to the center wavelength, attenuated as it is farther from the center wavelength, and is emitted to the outside of the organic EL element 100. In this way, the light L emitted from the organic EL element 100 has a narrow half-value width of the emission spectrum and improved color purity.
　マイクロキャビティ構造は、陰極および陽極を両端とする固定端反射による共振を利用している。そのため、「発光位置から陽極までの光路長が、素子外部に射出される所望の光の波長λの１／４の整数倍」であり、かつ「発光位置から陰極までの光路長が、素子外部に射出される所望の光の波長λの１／４の整数倍」である場合、所望のマイクロキャビティ構造を形成できる。 The microcavity structure utilizes resonance due to fixed-end reflection with the cathode and anode at both ends. Therefore, "the optical path length from the light emitting position to the anode is an integral multiple of 1/4 of the wavelength λ of the desired light emitted to the outside of the element", and "the optical path length from the light emitting position to the cathode is outside the element". If it is "an integral multiple of 1/4 of the wavelength λ of the desired light emitted into the light", the desired microcavity structure can be formed.
　本実施形態の有機ＥＬ素子１００は、上述したいずれかの１層または複数層に、上述した含フッ素重合体を含む。
　本実施形態の有機ＥＬ素子１００は、正孔注入層１１２と正孔輸送層１１３の少なくとも一方に、上述した含フッ素重合体を含むことが好ましい。正孔輸送層１１３が、正孔輸送材料の層の積層体である場合、各層のうち少なくとも１層に上述した含フッ素重合体を含む。
　また、本実施形態の有機ＥＬ素子１００は、電子輸送層１１５と電子注入層１１６の少なくとも一方に、上述した含フッ素重合体を含むことが好ましい。電子輸送層１１５が、電子輸送材料の層の積層体である場合、各層のうち少なくとも１層に上述した含フッ素重合体を含む。
　また、本実施形態の有機ＥＬ素子１００は、正孔注入層１１２と正孔輸送層１１３の少なくとも一方、および電子輸送層１１５と電子注入層１１６の少なくとも一方に、上述した含フッ素重合体を含むことが好ましい。 The organic EL device 100 of the present embodiment contains the above-mentioned fluorine-containing polymer in any one or more layers described above.
The organic EL device 100 of the present embodiment preferably contains the above-mentioned fluorine-containing polymer in at least one of the hole injection layer 112 and the hole transport layer 113. When the hole transport layer 113 is a laminate of layers of hole transport materials, at least one of the layers contains the above-mentioned fluorine-containing polymer.
Further, the organic EL element 100 of the present embodiment preferably contains the above-mentioned fluorine-containing polymer in at least one of the electron transport layer 115 and the electron injection layer 116. When the electron transport layer 115 is a laminate of layers of electron transport materials, at least one of the layers contains the above-mentioned fluorine-containing polymer.
Further, the organic EL device 100 of the present embodiment contains the above-mentioned fluorine-containing polymer in at least one of the hole injection layer 112 and the hole transport layer 113, and at least one of the electron transport layer 115 and the electron injection layer 116. Is preferable.
　上述した含フッ素重合体を含んだ各層は、これらの層が上述した含フッ素重合体を含まない場合と比べ低屈折率となる。そのため、本実施形態の有機ＥＬ素子１００は、光取出し効率が向上し、外部量子効率が向上する。これにより、本実施形態の有機ＥＬ素子１００は、上述した含フッ素重合体を含まない従来の有機ＥＬ素子と比べて、少ない投入電力で従来の有機ＥＬ素子と同等の発光量が得られる。
　また、上述した含フッ素重合体を含んだ各層は、耐熱性が高い。そのため、本実施形態の有機ＥＬ素子１００は、信頼性が高い有機ＥＬ素子１００となる。 Each layer containing the above-mentioned fluorine-containing polymer has a lower refractive index than the case where these layers do not contain the above-mentioned fluorine-containing polymer. Therefore, the organic EL element 100 of the present embodiment improves the light extraction efficiency and the external quantum efficiency. As a result, the organic EL element 100 of the present embodiment can obtain the same amount of light emission as the conventional organic EL element with a smaller input power as compared with the conventional organic EL element that does not contain the above-mentioned fluorine-containing polymer.
In addition, each layer containing the above-mentioned fluorine-containing polymer has high heat resistance. Therefore, the organic EL element 100 of the present embodiment is a highly reliable organic EL element 100.
　有機ＥＬ素子１００の耐熱性は、下記の方法で評価することができる。
＜耐熱性評価１＞
［導電性評価用の素子１の作製］
　２ｍｍ幅の帯状にＩＴＯ(酸化インジウムスズ）が成膜されたガラス基板を用いる。
　当該基板を中性洗剤、アセトン、イソプロパノールを用いて超音波洗浄し、さらにイソプロパノール中で煮沸洗浄した上で、オゾン処理によりＩＴＯ膜表面の付着物を除去する。
　洗浄後の基板を真空蒸着機内に置き、圧力１０－４Ｐａ以下に減圧した上で、基板上に三酸化モリブデンを蒸着する。蒸着速度は０．１ｎｍ／秒であり、５ｎｍ成膜して正孔注入層を作製する。 The heat resistance of the organic EL element 100 can be evaluated by the following method.
<Heat resistance evaluation 1>
[Manufacturing of element 1 for conducting conductivity evaluation]
A glass substrate on which ITO (indium tin oxide) is formed in a 2 mm wide strip is used.
The substrate is ultrasonically cleaned with a neutral detergent, acetone, and isopropanol, and then boiled and washed in isopropanol, and then the deposits on the surface of the ITO film are removed by ozone treatment.
The washed substrate is placed in a vacuum vapor deposition machine, the pressure is reduced to 10 -4 Pa or less, and molybdenum trioxide is vapor-deposited on the substrate. The vapor deposition rate is 0.1 nm / sec, and a 5 nm film is formed to prepare a hole injection layer.
　次いで、正孔注入層上にα－ＮＰＤと、含フッ素重合体と、を共蒸着する。２つの材料の合計の蒸着速度は０．２ｎｍ／秒であり、１００ｎｍ成膜して電荷輸送層を作製する。蒸着速度を調整し、電荷輸送層におけるα－ＮＰＤと含フッ素重合体の体積比を所望の比率とする。 Next, α-NPD and a fluorine-containing polymer are co-deposited on the hole injection layer. The total vapor deposition rate of the two materials is 0.2 nm / sec, and a 100 nm film is formed to prepare a charge transport layer. The vapor deposition rate is adjusted so that the volume ratio of α-NPD to the fluorine-containing polymer in the charge transport layer is a desired ratio.
　次いで、電荷輸送層上に２ｍｍ幅の帯状にアルミニウムを蒸着する。帯状のアルミニウム膜は、基板の垂直方向から見た視野においてＩＴＯ膜と直交させる。これにより、素子面積４ｍｍ２（＝ＩＴＯ膜２ｍｍ×アルミニウム膜２ｍｍ）の導電性評価用の素子１を得る。 Next, aluminum is deposited on the charge transport layer in the form of a strip having a width of 2 mm. The strip-shaped aluminum film is orthogonal to the ITO film in the field of view seen from the vertical direction of the substrate. As a result, an element 1 for evaluating conductivity having an element area of 4 mm 2 (= ITO film 2 mm × aluminum film 2 mm) is obtained.
［素子１の耐熱性評価］
　ソースメータ（アジレント・テクノロジー社製：Ｂ１５００Ａ）を用い、素子１のＩＴＯを陽極、アルミニウムを陰極として電圧を印加しながら電圧を変化させ、電圧毎に素子に流れる電流を測定し、電界（Ｅ）（単位：ＭＶ／ｃｍ）に対する電流密度（Ｊ）（単位：ｍＡ／ｃｍ２）を求める。
　なお、電界（Ｅ）は、電圧値を上記電荷輸送層の膜厚である１００ｎｍで割った値であり、電流密度（Ｊ）は、電流値を上記素子面積である４ｍｍ２で割った値である。 [Evaluation of heat resistance of element 1]
Using a source meter (Agilent Technology Co., Ltd .: B1500A), the voltage is changed while applying a voltage using ITO of element 1 as an anode and aluminum as a cathode, and the current flowing through the element is measured for each voltage to measure the electric field (E). The current density (J) (unit: mA / cm 2 ) with respect to (unit: MV / cm) is obtained.
The electric field (E) is a value obtained by dividing the voltage value by 100 nm, which is the film thickness of the charge transport layer, and the current density (J) is a value obtained by dividing the current value by the element area of 4 mm 2. be.
　次いで、Ｎ２雰囲気において、素子１を８０℃のホットプレート上で６０分加熱する。素子１を常温に戻した後、再度素子に流れる電流を測定し、電界（Ｅ）（単位：ＭＶ／ｃｍ）に対する電流密度（Ｊ）（単位：ｍＡ／ｃｍ２）を求める。
　次いで、Ｎ２雰囲気において、同じ素子１を９０℃のホットプレート上で６０分加熱する。素子１を常温に戻した後、再度素子に流れる電流を測定し、電界（Ｅ）（単位：ＭＶ／ｃｍ）に対する電流密度（Ｊ）（単位：ｍＡ／ｃｍ２）を求める。 Then, the N 2 atmosphere, heating 60 minutes element 1 at 80 ° C. on a hot plate. After returning the element 1 to room temperature, the current flowing through the element is measured again to obtain the current density (J) (unit: mA / cm 2) with respect to the electric field (E) (unit: MV / cm).
Then, the N 2 atmosphere, the same element 1 is heated 60 minutes at 90 ° C. on a hot plate. After returning the element 1 to room temperature, the current flowing through the element is measured again to obtain the current density (J) (unit: mA / cm 2) with respect to the electric field (E) (unit: MV / cm).
　得られた結果から、素子１の耐熱性を以下のように評価する。
　×：８０℃に加熱後、０．４ＭＶ／ｃｍの電流密度が初期の９０％未満
　△：９０℃に加熱後、０．４ＭＶ／ｃｍの電流密度が初期の９０％未満
　〇：９０℃に加熱後、０．４ＭＶ／ｃｍの電流密度が初期の９０％以上 From the obtained results, the heat resistance of the element 1 is evaluated as follows.
×: After heating to 80 ° C, the current density of 0.4 MV / cm is less than 90% of the initial value Δ: After heating to 90 ° C, the current density of 0.4 MV / cm is less than 90% of the initial value 〇: Heating to 90 ° C. After that, the current density of 0.4 MV / cm is 90% or more of the initial value.
＜耐熱性評価２＞
［導電性評価用の素子２の作製］
　三酸化モリブデンの代わりにＨＡＴ－ＣＮ，α－ＮＰＤの代わりにＨＴ２１１を用いたこと以外は、［導電性評価用の素子１の作製］と同様に行い、導電性評価用の素子２を作製する。 <Heat resistance evaluation 2>
[Manufacturing of element 2 for conducting conductivity evaluation]
HAT-CN was used instead of molybdenum trioxide, and HT211 was used instead of α-NPD. ..
［素子２の耐熱性評価］
　加熱温度を１００℃、１１０℃、１２０℃、１３０℃とし、加熱時間をそれぞれ１５分間とした以外は［素子１の耐熱性評価］と同様に行い、電界（Ｅ）（単位：ＭＶ／ｃｍ）に対する電流密度（Ｊ）（単位：ｍＡ／ｃｍ２）を求める。
　得られた結果から、素子２の耐熱性を以下のように評価する。
　×：１００℃に加熱後、０．４ＭＶ／ｃｍの電流密度が初期の９０％未満
　△：１１０℃に加熱後、０．４ＭＶ／ｃｍの電流密度が初期の９０％未満
　〇：１２０℃に加熱後、０．４ＭＶ／ｃｍの電流密度が初期の９０％未満
　〇〇：１３０℃に加熱後、０．４ＭＶ／ｃｍの電流密度が初期の９０％未満
　〇〇〇：１３０℃に加熱後、０．４ＭＶ／ｃｍの電流密度が初期の９０％以上 [Evaluation of heat resistance of element 2]
The heating temperature was set to 100 ° C., 110 ° C., 120 ° C., and 130 ° C., and the heating time was set to 15 minutes, respectively. The current density (J) (unit: mA / cm 2 ) with respect to is obtained.
From the obtained results, the heat resistance of the element 2 is evaluated as follows.
×: After heating to 100 ° C, the current density of 0.4 MV / cm is less than 90% of the initial value Δ: After heating to 110 ° C, the current density of 0.4 MV / cm is less than 90% of the initial value 〇: Heating to 120 ° C. After, the current density of 0.4 MV / cm is less than 90% of the initial value 〇 〇: After heating to 130 ° C, the current density of 0.4 MV / cm is less than 90% of the initial value 〇 〇 〇: After heating to 130 ° C, 0 .4 MV / cm current density is 90% or more of the initial value
　また、上述した含フッ素重合体は、製造時には、各層を構成する有機半導体と共蒸着した共蒸着膜として各層に導入するとよい。具体的には、例えば正孔注入層１１２と正孔輸送層１１３とにいずれも上述した含フッ素重合体を含ませる場合、正孔注入材料と含フッ素重合体とを共蒸着して共蒸着膜（第１膜）を形成した後、正孔輸送材料と含フッ素重合体とを共蒸着して共蒸着膜（第２膜）を形成するとよい。 Further, the above-mentioned fluorine-containing polymer may be introduced into each layer as a co-deposited film co-deposited with the organic semiconductors constituting each layer at the time of production. Specifically, for example, when the hole injection layer 112 and the hole transport layer 113 both contain the above-mentioned fluorine-containing polymer, the hole injection material and the fluorine-containing polymer are co-deposited to form a co-deposit film. After forming the (first film), the hole transport material and the fluorine-containing polymer may be co-deposited to form the co-deposited film (second film).
　以上のような構成の有機ＥＬ素子１００によれば、正孔注入層１１２と正孔輸送層１１３の少なくとも一方が上述した含フッ素重合体を含むことにより、外部量子効率が向上し、消費電力が少ない有機ＥＬ素子となる。 According to the organic EL device 100 having the above configuration, since at least one of the hole injection layer 112 and the hole transport layer 113 contains the above-mentioned fluorine-containing polymer, the external quantum efficiency is improved and the power consumption is increased. There are few organic EL elements.
［第３実施形態］
　図７は、本発明の第３実施形態に係る有機ＥＬ素子２００の説明図であり、図６に対応する図である。
　有機ＥＬ素子２００は、基板２１０、陽極２１１、正孔注入層１１２、正孔輸送層１１３、発光層１１４、電子輸送層１１５、電子注入層１１６、陰極２１７がこの順に積層した構造を有している。本実施形態の有機ＥＬ素子２００は、発光層１１４で生じた光Ｌが、陽極２１１および基板２１０を介して外部へ射出されるボトムエミッション方式を採用している。 [Third Embodiment]
FIG. 7 is an explanatory diagram of the organic EL element 200 according to the third embodiment of the present invention, and is a diagram corresponding to FIG.
The organic EL element 200 has a structure in which a substrate 210, an anode 211, a hole injection layer 112, a hole transport layer 113, a light emitting layer 114, an electron transport layer 115, an electron injection layer 116, and a cathode 217 are laminated in this order. There is. The organic EL element 200 of the present embodiment employs a bottom emission method in which the light L generated in the light emitting layer 114 is emitted to the outside via the anode 211 and the substrate 210.
　基板２１０は、光透過性を備えている。基板２１０の形成材料としては、ガラス、石英ガラス、窒化ケイ素等の無機物や、ポリイミド樹脂、アクリル樹脂、ポリカーボネート樹脂等の有機高分子（樹脂）を用いることができる。また、光透過性を有するならば、上記材料を積層または混合して形成された複合材料を用いることもできる。 The substrate 210 has light transmission. As the material for forming the substrate 210, an inorganic substance such as glass, quartz glass, or silicon nitride, or an organic polymer (resin) such as a polyimide resin, an acrylic resin, or a polycarbonate resin can be used. Further, if it has light transmission property, a composite material formed by laminating or mixing the above materials can also be used.
　陽極２１１は、基板２１０上に形成され、正孔輸送層１１３に正孔を供給する。陽極２１１の形成材料としては、ＩＴＯやＩＺＯ等の光透過性を有する導電性金属酸化物を用いることができる。 The anode 211 is formed on the substrate 210 and supplies holes to the hole transport layer 113. As the material for forming the anode 211, a conductive metal oxide having light transmittance such as ITO and IZO can be used.
　陰極２１７は、電子注入層１１６の上に形成されている。陰極２１７は、電子注入層１１６に電子を注入する機能を有する。また、陰極２１７は、発光層１１４において等方的に放射される光Ｌを反射し、陽極２１１の方へ向かわせる機能を有する。陰極２１７の形成材料としては、ＭｇＡｇ、Ａｇ、Ａｌ等を用いることができる。陰極２１７の表面にはＬｉＦ等のバッファー層が形成されていてもよい。
　陰極２１７の厚さは、特に制限されないが、３０～３００ｎｍが好ましい。陰極２１７の厚さは、例えば１００ｎｍである。 The cathode 217 is formed on the electron injection layer 116. The cathode 217 has a function of injecting electrons into the electron injecting layer 116. Further, the cathode 217 has a function of reflecting the light L emitted isotropically in the light emitting layer 114 and directing the light L toward the anode 211. As a material for forming the cathode 217, MgAg, Ag, Al and the like can be used. A buffer layer such as LiF may be formed on the surface of the cathode 217.
The thickness of the cathode 217 is not particularly limited, but is preferably 30 to 300 nm. The thickness of the cathode 217 is, for example, 100 nm.
　このような構成の有機ＥＬ素子２００においても、第２実施形態で示した有機ＥＬ素子１００と同様に、上述したいずれか１層または複数層に、上述した含フッ素重合体を含むことが好ましい。詳しくは、有機ＥＬ素子２００は、正孔注入層１１２と正孔輸送層１１３の少なくとも一方の層に、上述した含フッ素重合体を含むことが好ましい。
　また、有機ＥＬ素子２００は、電子輸送層１１５と電子注入層１１６の少なくとも一方の層に、上述した含フッ素重合体を含むことが好ましい。
　さらに、有機ＥＬ素子２００は、正孔注入層１１２と正孔輸送層１１３の少なくとも一方、および電子輸送層１１５と電子注入層１１６の少なくとも一方に、上述した含フッ素重合体を含むことが好ましい。
　これにより、有機ＥＬ素子２００は、含フッ素重合体を含まない従来の有機ＥＬ素子と比べて、光取出し効率が向上する。 Similarly to the organic EL element 100 shown in the second embodiment, the organic EL element 200 having such a configuration preferably contains the above-mentioned fluorine-containing polymer in any one or more layers described above. Specifically, the organic EL element 200 preferably contains the above-mentioned fluorine-containing polymer in at least one layer of the hole injection layer 112 and the hole transport layer 113.
Further, the organic EL element 200 preferably contains the above-mentioned fluorine-containing polymer in at least one layer of the electron transport layer 115 and the electron injection layer 116.
Further, the organic EL element 200 preferably contains the above-mentioned fluorine-containing polymer in at least one of the hole injection layer 112 and the hole transport layer 113, and at least one of the electron transport layer 115 and the electron injection layer 116.
As a result, the organic EL element 200 has improved light extraction efficiency as compared with the conventional organic EL element that does not contain a fluorine-containing polymer.
　以上のような構成の有機ＥＬ素子２００によっても、各層が上述した含フッ素重合体を含むことにより、外部量子効率が向上し、消費電力が少ない有機ＥＬ素子となる。
　また、上述した含フッ素重合体を含んだ各層は、耐熱性が高い。そのため、本実施形態の有機ＥＬ素子２００は、信頼性が高い有機ＥＬ素子２００となる。
　有機ＥＬ素子２００の耐熱性は、上述の有機ＥＬ素子１００の耐熱性と同様の方法で評価することができる。
　なお、有機ＥＬ素子１００または有機ＥＬ素子２００は、各層の間に、その他の機能層を配置してもよい。例えば、発光層と電荷輸送層の間に、正孔ブロック層や電子ブロック層を配置してもよいし、前述のマイクロキャビティ構造を形成するための調整層を配置してもよい。 Even with the organic EL device 200 having the above configuration, the external quantum efficiency is improved and the power consumption is low because each layer contains the above-mentioned fluorine-containing polymer.
In addition, each layer containing the above-mentioned fluorine-containing polymer has high heat resistance. Therefore, the organic EL element 200 of the present embodiment is a highly reliable organic EL element 200.
The heat resistance of the organic EL element 200 can be evaluated by the same method as the heat resistance of the organic EL element 100 described above.
The organic EL element 100 or the organic EL element 200 may have other functional layers arranged between the layers. For example, a hole block layer or an electron block layer may be arranged between the light emitting layer and the charge transport layer, or an adjusting layer for forming the above-mentioned microcavity structure may be arranged.
　また、有機ＥＬ素子１００または有機ＥＬ素子２００において、光射出方向に量子ドットを含む波長変換層を配置してもよい。このような波長変換層を有することにより、射出する光の色純度を向上させた有機ＥＬ素子となる。
　有機ＥＬ素子１００または有機ＥＬ２００において、発光層１１４の形成材料として量子ドットを用いてもよい。
　量子ドットとは、量子力学に従う独特な光学特性を持つナノスケールの半導体結晶を指す。量子ドットは、通常、２～１０ｎｍの直径の単結晶粒子である。量子ドットは、結晶サイズ（＝粒径）に応じてバンドギャップが変化するため、粒径を調整することでバンドギャップを調整することができ、所望の発光波長が得られる。 Further, in the organic EL element 100 or the organic EL element 200, a wavelength conversion layer containing quantum dots may be arranged in the light emission direction. By having such a wavelength conversion layer, it becomes an organic EL element in which the color purity of the emitted light is improved.
In the organic EL element 100 or the organic EL 200, quantum dots may be used as a material for forming the light emitting layer 114.
Quantum dots refer to nanoscale semiconductor crystals with unique optical properties that follow quantum mechanics. Quantum dots are usually single crystal particles with a diameter of 2-10 nm. Since the bandgap of the quantum dot changes according to the crystal size (= particle size), the bandgap can be adjusted by adjusting the particle size, and a desired emission wavelength can be obtained.
　量子ドットとしては、溶液に分散可能なコロイド状量子ドットを用いることも可能である。このようなコロイド状量子ドットは、一般的なウェットコーティング技術を用いて成膜することが出来る。
　量子ドットの種類は特に制限はなく、ペロブスカイト量子ドット、炭素系量子ドット、合金型量子ドット、コア・シェル型量子ドット、コア型量子ドットを用いることが出来る。 As the quantum dots, colloidal quantum dots that can be dispersed in a solution can also be used. Such colloidal quantum dots can be formed by using a general wet coating technique.
The type of quantum dots is not particularly limited, and perovskite quantum dots, carbon-based quantum dots, alloy-type quantum dots, core-shell type quantum dots, and core-type quantum dots can be used.
　また、上述の実施形態においては、有機光電子素子として有機ＥＬ素子を例示して説明したが、本発明の含フッ素重合体を含む膜が適用される有機光電子素子は、有機ＥＬ素子に限らない。
　本発明の有機光電子素子は、例えば有機半導体レーザーであってもよい。有機半導体レーザーとしては公知の構成を採用できる。有機半導体レーザーを構成する有機半導体からなるいずれかの膜に上述の含フッ素重合体を含む膜を採用することにより、外部量子効率が向上した有機半導体レーザーとなる。
　また、本発明の有機光電子素子は、例えば、光センサ、太陽電池などの受光素子であってもよい。光センサおよび太陽電池としては公知の構成を採用できる。
　光センサおよび太陽電池を構成する有機半導体からなるいずれかの膜に上述の含フッ素重合体を含む膜を採用することにより、検出性能を向上させた光センサや、発電効率を向上させた太陽電池となる。 Further, in the above-described embodiment, the organic EL device has been described as an example of the organic photoelectronic device, but the organic photoelectronic device to which the film containing the fluorine-containing polymer of the present invention is applied is not limited to the organic EL device.
The organic photoelectronic device of the present invention may be, for example, an organic semiconductor laser. A known configuration can be adopted as the organic semiconductor laser. By adopting a film containing the above-mentioned fluorine-containing polymer as one of the films made of organic semiconductors constituting the organic semiconductor laser, the organic semiconductor laser having improved external quantum efficiency can be obtained.
Further, the organic photoelectron element of the present invention may be, for example, a light receiving element such as an optical sensor or a solar cell. Known configurations can be adopted for the optical sensor and the solar cell.
An optical sensor with improved detection performance and a solar cell with improved power generation efficiency by adopting a film containing the above-mentioned fluorine-containing polymer as one of the films composed of an optical sensor and an organic semiconductor constituting a solar cell. It becomes.
　以上、添付図面を参照しながら本発明に係る好適な実施の形態例について説明したが、本発明は係る例に限定されない。上述した例において示した各構成部材の諸形状や組み合わせ等は一例であって、本発明の主旨から逸脱しない範囲において設計要求等に基づき種々変更可能である。 Although the preferred embodiment of the present invention has been described above with reference to the accompanying drawings, the present invention is not limited to such an example. The various shapes and combinations of the constituent members shown in the above-mentioned examples are examples, and can be variously changed based on design requirements and the like within a range that does not deviate from the gist of the present invention.
　以下に本発明を実施例により説明するが、本発明はこれらの実施例に限定されるものではない。 The present invention will be described below with reference to examples, but the present invention is not limited to these examples.
＜評価方法＞
　本実施形態においては、以下の各方法により評価を行った。 <Evaluation method>
In this embodiment, evaluation was performed by each of the following methods.
［含フッ素重合体の真空下における熱重量減少率の測定］
　真空示差熱天秤（アドバンス理工社製：ＶＰＥ－９０００）を用いて測定した。含フッ素重合体５０ｍｇを内径７ｍｍのセルに仕込み、１×１０－３Ｐａの真空度にて、室温から５００℃まで毎分２℃で昇温させた際の、含フッ素重合体の初期重量（５０ｍｇ）に対する重量減少率（％）を測定した。
　重量減少率が１００％となる温度（Ｔｄ１００）、重量減少率が１０％となる温度（Ｔｄ１０）および重量減少率が９０％となる温度（Ｔｄ９０）を求めた。 [Measurement of thermogravimetric reduction rate of fluorine-containing polymer under vacuum]
The measurement was performed using a vacuum differential thermal balance (manufactured by Advance Riko Co., Ltd .: VPE-9000). Were charged fluoropolymer 50mg to the cells of the inner diameter 7 mm, at 1 × 10 -3 Pa vacuum degree, when the temperature was raised per minute 2 ℃ to 500 ° C. from room temperature, the initial weight of the fluoropolymer ( The weight loss rate (%) with respect to 50 mg) was measured.
The temperature at which the weight loss rate was 100% (T d100 ), the temperature at which the weight loss rate was 10% (T d10 ), and the temperature at which the weight loss rate was 90% (T d90 ) were determined.
［融点の測定］
　示差走査熱量計（ＮＥＴＺＳＣＨ製：ＤＳＣ　２０４　Ｆ１　Ｐｈｏｅｎｉｘ）を用いて測定した。含フッ素重合体９ｍｇを試料容器に仕込み、－７０℃から３５０まで毎分１０℃で昇温させた際の熱容量を測定し、得られた融解ピークより融点を求めた。 [Measurement of melting point]
The measurement was performed using a differential scanning calorimeter (manufactured by NETZSCH: DSC 204 F1 Phoenix). 9 mg of the fluorine-containing polymer was charged in a sample container, the heat capacity when the temperature was raised from −70 ° C. to 350 at 10 ° C. per minute was measured, and the melting point was determined from the obtained melting peak.
［貯蔵弾性率の測定］
　本実施形態において、貯蔵弾性率は、動的粘弾性測定装置（アントンパール社製、ＭＣＲ５０２）、および粘弾性測定装置用加熱炉（アントンパール社製、ＣＴＤ４５０）を用いて測定する値を採用した。
　具体的には、試料（含フッ素重合体）を融点以上に加熱した後、定速降温モードで２℃／分で降温させた。上記測定装置を用い、歪み０．０１％、周波数１Ｈｚの条件で貯蔵弾性率（Ｇ’）を測定し、２５℃におけるＧ’およびＧ’が１×１０６Ｐａ未満になる温度を求めた。 [Measurement of storage elastic modulus]
In the present embodiment, the storage elastic modulus adopts a value measured using a dynamic viscoelasticity measuring device (manufactured by Anton Pearl Co., Ltd., MCR502) and a heating furnace for a viscoelasticity measuring device (manufactured by Anton Pearl Co., Ltd., CTD450). ..
Specifically, the sample (fluorine-containing polymer) was heated to a temperature equal to or higher than the melting point, and then cooled at 2 ° C./min in a constant-speed temperature lowering mode. Using the above measuring device, the storage elastic modulus (G') was measured under the conditions of a strain of 0.01% and a frequency of 1 Hz, and the temperature at which G'and G'at 25 ° C. became less than 1 × 10 6 Pa was determined.
＜含フッ素重合体の合成＞
　評価に用いた含フッ素重合体は、以下のように合成した。
［合成例１］
　内容積１．３５１Ｌのジャケット付きの重合槽（ステンレス鋼製）を脱気し、重合槽内に、１，１，２，２－テトラフルオロエチル－２，２，２－トリフルオロエチルエーテル（ＡＥ－３０００、ＡＧＣ社製）を７０１ｇ、ペルフルオロプロピルビニルエーテル（ＰＰＶＥ）を５７ｇ、テトラフルオロエチレン（ＴＦＥ）を１０８ｇ、メタノールを３５．７ｇ、それぞれ秤量して仕込んだ。 <Synthesis of Fluorine-Containing Polymer>
The fluorine-containing polymer used for the evaluation was synthesized as follows.
[Synthesis Example 1]
A polymerization tank (made of stainless steel) with a jacket having an internal volume of 1.351 L is degassed, and 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether (AE) is placed in the polymerization tank. 701 g of -3000 (manufactured by AGC), 57 g of perfluoropropyl vinyl ether (PPVE), 108 g of tetrafluoroethylene (TFE), and 35.7 g of methanol were weighed and charged.
　重合槽の温度を６０℃に保持して、ｔ－ブチルパーオキシピバレート（ＰＢＰＶ）の０．５３質量％溶液（溶媒：ＡＥ－３０００）の１８．９ｍＬを仕込み、重合を開始させた。
　重合中、重合の進行に伴い重合圧力が低下するため、重合圧力がほぼ一定になるように重合槽内にＴＦＥを連続的に導入した。重合圧力は、１．０４±０．０４ＭＰａＧ（ゲージ圧）に保持した。
　なお、「ゲージ圧」とは、大気圧を０ＭＰａＧとする相対圧力であり、真空をゼロとする絶対圧力との差を指す。 The temperature of the polymerization tank was maintained at 60 ° C., and 18.9 mL of a 0.53 mass% solution (solvent: AE-3000) of t-butylperoxypivalate (PBPV) was charged to initiate polymerization.
Since the polymerization pressure decreases as the polymerization progresses during the polymerization, TFE was continuously introduced into the polymerization tank so that the polymerization pressure became substantially constant. The polymerization pressure was maintained at 1.04 ± 0.04 MPaG (gauge pressure).
The "gauge pressure" is a relative pressure with an atmospheric pressure of 0 MPaG, and refers to a difference from an absolute pressure with a vacuum of zero.
　ＴＦＥの導入量が１２１ｇになった時点で重合を終了させ、含フッ素重合体を得た。得られた重合体の組成は、ＰＰＶＥ単位：ＴＦＥ単位＝２：９８（モル％）であった。 When the amount of TFE introduced reached 121 g, the polymerization was terminated to obtain a fluorine-containing polymer. The composition of the obtained polymer was PPVE unit: TFE unit = 2:98 (mol%).
　次いで、得られた重合体を３３０℃のオーブンで加熱した後、メタノールに浸漬し、７５℃のオーブンで４０時間加熱することで、末端基をメチルエステル基に置換し、含フッ素重合体Ａを得た。 Next, the obtained polymer was heated in an oven at 330 ° C., immersed in methanol, and heated in an oven at 75 ° C. for 40 hours to replace the terminal group with a methyl ester group to obtain the fluorine-containing polymer A. Obtained.
　得られた含フッ素重合体Ａの４４ｇを上述したガラスチューブ式の昇華精製装置の原料仕込み部に仕込み、捕集部内を３．０×１０－３Ｐａに減圧した。次いで、原料仕込み部を３３０℃まで徐々に加温し、含フッ素重合体Ａを昇華させた。昇華精製装置では、捕集部を仕込み部に近い側から３１０℃、２８０℃、２５０℃の設定温度で加熱した。
　このうち、設定温度２８０℃の捕集部に析出させた物質を回収し、精製した４ｇの含フッ素重合体Ａ１を得た。 44 g of the obtained fluorine-containing polymer A was charged into the raw material charging section of the above-mentioned glass tube type sublimation purification apparatus, and the pressure inside the collecting section was reduced to 3.0 × 10 -3 Pa. Next, the raw material charging portion was gradually heated to 330 ° C. to sublimate the fluorine-containing polymer A. In the sublimation purification apparatus, the collecting portion was heated at set temperatures of 310 ° C., 280 ° C., and 250 ° C. from the side closer to the charging portion.
Of these, the substance precipitated in the collection section at the set temperature of 280 ° C. was recovered to obtain 4 g of the purified fluorine-containing polymer A1.
［合成例２］
　ＡＥ－３０００を６４９ｇ、ＰＰＶＥを１５２ｇ、ＴＦＥを１０９ｇ、メタノールを１５．５ｇ、ＰＢＰＶの０．７９質量％溶液（溶媒：ＡＥ－３０００）の１８．９ｍＬ用いたこと以外は合成例１と同様にして、含フッ素重合体を得た。
　得られた含フッ素重合体の組成は、ＰＰＶＥ単位：ＴＦＥ単位＝４：９６（モル％）であった。
　次いで、合成例１と同様の条件で含フッ素重合体の末端基をメチルエステル基に置換し、含フッ素重合体Ｂを得た。 [Synthesis Example 2]
Same as Synthesis Example 1 except that 649 g of AE-3000, 152 g of PPVE, 109 g of TFE, 15.5 g of methanol, and 18.9 mL of a 0.79 mass% solution of PBPV (solvent: AE-3000) were used. To obtain a fluorine-containing polymer.
The composition of the obtained fluorine-containing polymer was PPVE unit: TFE unit = 4: 96 (mol%).
Next, the terminal group of the fluorine-containing polymer was replaced with a methyl ester group under the same conditions as in Synthesis Example 1 to obtain a fluorine-containing polymer B.
　含フッ素重合体Ｂを２０ｇ用いたこと以外は合成例１と同様にして含フッ素重合体Ｂを昇華させた。設定温度２５０℃の捕集部に析出させた物質を回収し、精製した２ｇの含フッ素重合体Ｂ１を得た。 The fluorinated polymer B was sublimated in the same manner as in Synthesis Example 1 except that 20 g of the fluorinated polymer B was used. The substance precipitated in the collection section at a set temperature of 250 ° C. was recovered to obtain 2 g of purified fluorine-containing polymer B1.
　また、得られた含フッ素重合体Ｂの２０ｇを超臨界抽出装置の圧力容器に仕込み、二酸化炭素による超臨界抽出を行った。
　抽出温度を４０℃、抽出圧力３０ＭＰａ、二酸化炭素流量３０ｍｌ／分で（条件１）０．２ｇを抽出した後、抽出温度を８０℃、抽出圧力を６０ＭＰａに上げ、さらにエントレーナーとしてＡＣ－２０００（ＡＧＣ社製）を二酸化炭素に対して１０体積％の比率で用いて（条件２）１．４ｇの抽出物を得た。
　条件２で得られた抽出物を、含フッ素重合体Ｂ２とした。 Further, 20 g of the obtained fluorine-containing polymer B was charged into a pressure vessel of a supercritical extraction device, and supercritical extraction was performed with carbon dioxide.
After extracting 0.2 g (Condition 1) at an extraction temperature of 40 ° C., an extraction pressure of 30 MPa, and a carbon dioxide flow rate of 30 ml / min, the extraction temperature was raised to 80 ° C. and the extraction pressure was increased to 60 MPa. (Manufactured by AGC) was used at a ratio of 10% by volume with respect to carbon dioxide (Condition 2) to obtain 1.4 g of an extract.
The extract obtained under Condition 2 was designated as a fluorine-containing polymer B2.
［合成例３］
　合成例２と同様にして製造した含フッ素重合体を３３０℃のオーブンで加熱した後、特開平１１－１５２３１０号公報の段落［００４０］に記載の方法で処理し、フッ素ガスにより含フッ素重合体の末端基を－ＣＦ３基に置換して、含フッ素重合体Ｃを得た。
　原料仕込み部を３６０℃まで徐々に加温したこと以外は合成例１と同様にして含フッ素重合体Ｃを昇華させた。設定温度２５０℃および２８０℃の捕集部に析出させた物質を回収し、精製した６ｇの含フッ素重合体Ｃ１を得た。 [Synthesis Example 3]
The fluorine-containing polymer produced in the same manner as in Synthesis Example 2 is heated in an oven at 330 ° C., treated by the method described in paragraph [0040] of JP-A-11-152310, and the fluorine-containing polymer is treated with fluorine gas. The terminal group of −CF was replaced with 3 groups of −CF to obtain a fluorine-containing polymer C.
The fluorine-containing polymer C was sublimated in the same manner as in Synthesis Example 1 except that the raw material preparation portion was gradually heated to 360 ° C. The substance precipitated in the collection section at the set temperature of 250 ° C. and 280 ° C. was recovered to obtain 6 g of purified fluorine-containing polymer C1.
［合成例４］
　内容積１００６ｍＬのステンレス製オートクレーブに、ＰＰＶＥを５７．９ｇ、ＡＣ２０００（ＡＧＣ社製）を７６７ｇ、メタノールを４．１３ｇ、アゾビスイソブチロニトリル（ＡＩＢＮ）を１．２４ｇ仕込み、液体窒素で凍結脱気をした。
　オートクレーブを７０℃に昇温した後、オートクレーブ内にＴＦＥを４８．４ｇ導入し、重合反応を開始させた。重合の進行により、オートクレーブ内の圧力が低下するため、ＴＦＥを連続的に供給し、オートクレーブの温度と圧力を一定に保持しながら重合させた。重合開始から５時間後にオートクレーブを冷却して重合反応を停止し、系内のガスを排出して反応溶液を得た。 [Synthesis Example 4]
In a stainless steel autoclave with an internal volume of 1006 mL, 57.9 g of PPVE, 767 g of AC2000 (manufactured by AGC), 4.13 g of methanol, and 1.24 g of azobisisobutyronitrile (AIBN) were charged and frozen in liquid nitrogen. I was worried.
After the temperature of the autoclave was raised to 70 ° C., 48.4 g of TFE was introduced into the autoclave to start the polymerization reaction. Since the pressure in the autoclave decreases as the polymerization progresses, TFE was continuously supplied and the polymerization was carried out while keeping the temperature and pressure of the autoclave constant. Five hours after the start of the polymerization, the autoclave was cooled to stop the polymerization reaction, and the gas in the system was discharged to obtain a reaction solution.
　反応溶液にメタノールを８００ｇ加えて混合し反応溶液に溶解する重合体を析出させた後、層分離させ、重合体が分散している下層を回収した。得られた重合体の分散液を８０℃で１６時間温風乾燥し、次に１００℃で１６時間真空乾燥して、含フッ素重合体を１９ｇ得た。
　得られた含フッ素重合体の組成は、ＰＰＶＥ単位：ＴＦＥ単位＝６：９４（モル％）であった。 800 g of methanol was added to the reaction solution and mixed to precipitate a polymer dissolved in the reaction solution, followed by layer separation, and the lower layer in which the polymer was dispersed was recovered. The dispersion of the obtained polymer was dried with warm air at 80 ° C. for 16 hours and then vacuum dried at 100 ° C. for 16 hours to obtain 19 g of a fluorine-containing polymer.
The composition of the obtained fluorine-containing polymer was PPVE unit: TFE unit = 6: 94 (mol%).
　次いで、合成例１と同様にして含フッ素重合体の末端基をメチルエステル基に置換し、含フッ素重合体Ｄを得た。
　合成例１と同様にして含フッ素重合体Ｄを昇華させた。設定温度２５０℃および２８０℃の捕集部に析出させた物質を回収し、精製した５ｇの含フッ素重合体Ｄ１を得た。 Next, the terminal group of the fluorine-containing polymer was replaced with a methyl ester group in the same manner as in Synthesis Example 1 to obtain a fluorine-containing polymer D.
The fluorine-containing polymer D was sublimated in the same manner as in Synthesis Example 1. The substance precipitated in the collection section at the set temperature of 250 ° C. and 280 ° C. was recovered to obtain 5 g of the purified fluorine-containing polymer D1.
［合成例５］
　ＰＰＶＥを６９．４ｇ、メタノールを４．１８ｇ、ＡＩＢＮを１．２６ｇ用いたこと以外は、合成例４と同様にして、含フッ素重合体を得た。
　得られた含フッ素重合体の組成は、ＰＰＶＥ単位：ＴＦＥ単位＝８：９２（モル％）であった。 [Synthesis Example 5]
A fluorine-containing polymer was obtained in the same manner as in Synthesis Example 4, except that 69.4 g of PPVE, 4.18 g of methanol, and 1.26 g of AIBN were used.
The composition of the obtained fluorine-containing polymer was PPVE unit: TFE unit = 8:92 (mol%).
　次いで、合成例３と同様の条件で含フッ素重合体の末端基を－ＣＦ３基に置換して、含フッ素重合体Ｅを得た。
　合成例２と同様にして含フッ素重合体Ｅを昇華させ、精製した４ｇの含フッ素重合体Ｅ１を得た。 Next, the terminal group of the fluorine-containing polymer was replaced with 3 -CF groups under the same conditions as in Synthesis Example 3 to obtain a fluorine-containing polymer E.
The fluorine-containing polymer E was sublimated in the same manner as in Synthesis Example 2 to obtain 4 g of the purified fluorine-containing polymer E1.
［合成例６］
　ＰＰＶＥを７８．９ｇ、メタノールを４．２３ｇ、ＡＩＢＮを１．２７ｇ用いたこと以外は、合成例４と同様にして、含フッ素重合体を得た。
　得られた含フッ素重合体の組成は、ＰＰＶＥ単位：ＴＦＥ単位＝９：９１（モル％）であった。 [Synthesis Example 6]
A fluorine-containing polymer was obtained in the same manner as in Synthesis Example 4, except that 78.9 g of PPVE, 4.23 g of methanol and 1.27 g of AIBN were used.
The composition of the obtained fluorine-containing polymer was PPVE unit: TFE unit = 9:91 (mol%).
　次いで、合成例１と同様にして含フッ素重合体の末端基をメチルエステル基に置換し、含フッ素重合体Ｆを得た。
　合成例１と同様にして含フッ素重合体Ｆを昇華させ、精製した４ｇの含フッ素重合体Ｆ１を得た。 Then, the terminal group of the fluorine-containing polymer was replaced with a methyl ester group in the same manner as in Synthesis Example 1 to obtain a fluorine-containing polymer F.
The fluorine-containing polymer F was sublimated in the same manner as in Synthesis Example 1 to obtain 4 g of the purified fluorine-containing polymer F1.
［合成例７］
　ＰＰＶＥを８５．９ｇ、メタノールを４．２７ｇ、ＡＩＢＮを１．２８ｇ用いたこと以外は、合成例４と同様にして、含フッ素重合体を得た。
　得られた含フッ素重合体の組成は、ＰＰＶＥ単位：ＴＦＥ単位＝１０：９０（モル％）であった。 [Synthesis Example 7]
A fluorine-containing polymer was obtained in the same manner as in Synthesis Example 4, except that 85.9 g of PPVE, 4.27 g of methanol, and 1.28 g of AIBN were used.
The composition of the obtained fluorine-containing polymer was PPVE unit: TFE unit = 10:90 (mol%).
　次いで、合成例３と同様の条件で含フッ素重合体の末端基を－ＣＦ３基に置換して、含フッ素重合体Ｇを得た。
　合成例３と同様にして含フッ素重合体Ｇを昇華させた。設定温度２５０℃、２８０℃および３１０℃の捕集部に析出させた物質を回収し、精製した６ｇの含フッ素重合体Ｇ１を得た。 Next, the terminal group of the fluorine-containing polymer was replaced with 3 -CF groups under the same conditions as in Synthesis Example 3 to obtain a fluorine-containing polymer G.
The fluorine-containing polymer G was sublimated in the same manner as in Synthesis Example 3. The substance precipitated in the collection section at the set temperature of 250 ° C., 280 ° C. and 310 ° C. was recovered to obtain 6 g of the purified fluorine-containing polymer G1.
［合成例８］
　ＰＰＶＥを１５２．９ｇ、メタノールを２．４０ｇ、ＡＩＢＮを１．１５ｇ、ＴＦＥを５６．３ｇ用いたこと以外は、合成例４と同様にして、含フッ素重合体を得た。
　得られた含フッ素重合体の組成は、ＰＰＶＥ単位：ＴＦＥ単位＝１４：８６（モル％）であった。 [Synthesis Example 8]
A fluorine-containing polymer was obtained in the same manner as in Synthesis Example 4, except that 152.9 g of PPVE, 2.40 g of methanol, 1.15 g of AIBN, and 56.3 g of TFE were used.
The composition of the obtained fluorine-containing polymer was PPVE unit: TFE unit = 14:86 (mol%).
　次いで、得られた含フッ素重合体を３３０℃のオーブンで加熱した後、メタノールに浸漬し、７５℃のオーブンで４０時間加熱することで、末端基をメチルエステル基に置換し、含フッ素重合体Ｈを得た。
　合成例１と同様にして含フッ素重合体Ｈを昇華させ、精製した４ｇの含フッ素重合体Ｈ１を得た。 Next, the obtained fluorine-containing polymer was heated in an oven at 330 ° C., then immersed in methanol and heated in an oven at 75 ° C. for 40 hours to replace the terminal group with a methyl ester group, and the fluorine-containing polymer was used. I got H.
The fluorine-containing polymer H was sublimated in the same manner as in Synthesis Example 1 to obtain 4 g of the purified fluorine-containing polymer H1.
［合成例９］
　ペルフルオロ（３－ブテニルビニルエーテル）を３０ｇ、ＡＣ２０００（ＡＧＣ社製）を３０ｇ、メタノールを０．５ｇ、ジイソプロピルペルオキシジカーボネート（ＩＰＰ）を０．４４ｇを秤量し、内容積５０ｍｌのガラス製反応器に仕込んだ。反応器内を高純度窒素ガスにて置換した後、４０℃に加熱して２４時間重合を行った。
　得られた溶液を、６６６Ｐａ（絶対圧）、５０℃の条件で脱溶し、重合体を２８ｇ得た。 [Synthesis Example 9]
Weigh 30 g of perfluoro (3-butenyl vinyl ether), 30 g of AC2000 (manufactured by AGC), 0.5 g of methanol, and 0.44 g of diisopropyl peroxydicarbonate (IPP) into a glass reactor with an internal volume of 50 ml. I prepared it. After replacing the inside of the reactor with high-purity nitrogen gas, the mixture was heated to 40 ° C. and polymerized for 24 hours.
The obtained solution was desolubilized under the conditions of 666 Pa (absolute pressure) and 50 ° C. to obtain 28 g of a polymer.
　次いで、得られた重合体を３００℃のオーブンで加熱した後、メタノールに浸漬し、７５℃のオーブンで２０時間加熱することで、末端基をメチルエステル基に置換し、含フッ素重合体Ｉを得た。
　合成例４と同様にして含フッ素重合体Ｉを昇華精製し、精製した４ｇの含フッ素重合体Ｉ１を得た。 Next, the obtained polymer was heated in an oven at 300 ° C., then immersed in methanol and heated in an oven at 75 ° C. for 20 hours to replace the terminal group with a methyl ester group to obtain the fluorine-containing polymer I. Obtained.
The fluorine-containing polymer I was sublimated and purified in the same manner as in Synthesis Example 4 to obtain 4 g of the purified fluorine-containing polymer I1.
［合成例１０］
　内容積１．３５１Ｌのジャケット付きの重合槽（ステンレス鋼製）を脱気し、重合槽内に、Ｒ１１３（１，１，２－トリクロロ－１，２，２－トリフルオロエタン、ＡＧＣ社製）３３１ｇと、メタノール１．１ｇと、ヘキサフルオロプロペン（ＨＦＰ）７６５ｇを仕込んだ。さらに、重合槽内に、ＴＦＥを温度５０℃で１．３４ＭＰａＧとなるよう仕込んだ。
　次いで、ビス（ペルフルオロブチリル）ペルオキシドの１．５質量％溶液（溶媒：Ｒ１１３）を５４．７ｍｌ仕込み、重合を開始させた。 [Synthesis Example 10]
A polymerization tank (made of stainless steel) with a jacket with an internal volume of 1.351 L is degassed, and R113 (1,1,2-trichloro-1,2,2-trifluoroethane, manufactured by AGC) is placed in the polymerization tank. 331 g, 1.1 g of methanol, and 765 g of hexafluoropropene (HFP) were charged. Further, TFE was charged in the polymerization tank so as to have a temperature of 1.34 MPaG at a temperature of 50 ° C.
Next, 54.7 ml of a 1.5% by mass solution (solvent: R113) of bis (perfluorobutyryl) peroxide was charged to initiate polymerization.
　重合の進行に伴い重合槽内の圧力が低下するため、重合圧力がほぼ一定になるようにＴＦＥを連続的に仕込んだ。重合圧力は、１．３４ＭＰａＧに保持した。
　重合槽内にビス（ペルフルオロブチリル）ペルオキシドの１．５質量％溶液（溶媒：Ｒ１１３）を間欠で仕込み、ＴＦＥが８６ｇ消費された時点で重合を終了させ、含フッ素共重合体Ｊを得た。ＴＦＥの消費量は、ＴＦＥのガスボンベの質量減少量から求めた。 Since the pressure in the polymerization tank decreases as the polymerization progresses, TFE was continuously charged so that the polymerization pressure became almost constant. The polymerization pressure was maintained at 1.34 MPaG.
A 1.5% by mass solution (solvent: R113) of bis (perfluorobutyryl) peroxide was intermittently charged in the polymerization tank, and the polymerization was terminated when 86 g of TFE was consumed to obtain a fluorine-containing copolymer J. .. The amount of TFE consumed was determined from the amount of mass loss of the TFE gas cylinder.
　得られた含フッ素重合体Ｊの組成は、ＨＦＰ単位：ＴＦＥ単位＝８：９２（モル％）であった。
　合成例４と同様にして含フッ素重合体Jを昇華させ、精製した４ｇの含フッ素重合体Ｊ１を得た。 The composition of the obtained fluorine-containing polymer J was HFP unit: TFE unit = 8:92 (mol%).
The fluorine-containing polymer J was sublimated in the same manner as in Synthesis Example 4 to obtain 4 g of the purified fluorine-containing polymer J1.
　また、市販の含フッ素重合体として、ＴＦＥとペルフルオロアルキルビニルエーテルとの共重合体（ＰＦＡ）である以下の材料を用いた。
　Ｆｌｕｏｎ ＰＦＡ：ＡＧＣ社製　Ｆｌｕｏｎ ＰＦＡ　Ｐ－６３ Further, as a commercially available fluorine-containing polymer, the following material, which is a copolymer (PFA) of TFE and perfluoroalkyl vinyl ether, was used.
Fluoron PFA: AGC's Fluoron PFA P-63
　合成した含フッ素重合体について、上述の方法で物性を測定した。測定した物性を表１に示す。
Figure JPOXMLDOC01-appb-T000003
 The physical properties of the synthesized fluorine-containing polymer were measured by the above-mentioned method. The measured physical properties are shown in Table 1.
Figure JPOXMLDOC01-appb-T000003
　表１に示したとおり、含フッ素樹脂Ａ１～Ｇ１およびＪ１は、上述の実施形態で示した要件（１）～（３）を満たすが、含フッ素重合体Ｂ、ＨおよびＦｌｕｏｎ ＰＦＡは要件（２）、（３）を、含フッ素重合体Ｉ１、Ｈ１およびＨは要件（１）を満たしていないことが分かる。なお、含フッ素重合体Ｉ１は、非晶性であり結晶性を有さないことから、融点は検出されなかった。 As shown in Table 1, the fluorine-containing resins A1 to G1 and J1 satisfy the requirements (1) to (3) shown in the above-described embodiment, while the fluorine-containing polymers B, H and FluonPFA satisfy the requirement (2). ), (3), it can be seen that the fluorine-containing polymers I1, H1 and H do not satisfy the requirement (1). Since the fluorine-containing polymer I1 is amorphous and has no crystallinity, its melting point was not detected.
　表１に示した含フッ素重合体を用い、以下評価１～５を行った。
＜評価１：蒸着時のチャンバー圧変化＞
［蒸着時のチャンバー圧変化の評価法］
　真空蒸着機に含フッ素重合体を０．１g仕込み、チャンバー内の圧力を１０－４Ｐａ以下に減圧した上で、含フッ素重合体を蒸着速度０．１ｎｍ／秒で２００ｎｍ成膜した。この際にチャンバー内の圧力をモニターし、蒸着時における圧力の最大値を計測した。計測値を用い、下記計算式より圧力の上昇倍率を求めた。
　蒸着時のチャンバー圧力の上昇倍率＝蒸着中の最大圧力／蒸着前の初期圧力
　チャンバー圧力の上昇倍率が２倍以下である含フッ素重合体は「良品」と評価し、上昇倍率が２倍を超える含フッ素重合体は「不良」と評価した。 Evaluations 1 to 5 were carried out below using the fluorine-containing polymers shown in Table 1.
<Evaluation 1: Change in chamber pressure during vapor deposition>
[Evaluation method of chamber pressure change during vapor deposition]
0.1 g of the fluorine-containing polymer was charged into a vacuum vapor deposition machine, the pressure in the chamber was reduced to 10 -4 Pa or less, and then the fluorine-containing polymer was deposited at a vapor deposition rate of 0.1 nm / sec to 200 nm. At this time, the pressure in the chamber was monitored, and the maximum value of the pressure at the time of vapor deposition was measured. Using the measured values, the pressure increase rate was calculated from the following formula.
Increase ratio of chamber pressure during vapor deposition = Maximum pressure during vapor deposition / Initial pressure before vapor deposition Fluorine-containing polymers whose chamber pressure increase ratio is 2 times or less are evaluated as "good products" and the increase ratio exceeds 2 times. The fluorine-containing polymer was evaluated as "defective".
＜評価２：屈折率＞
［屈折率測定用試料の作製］
　シリコン基板上に、有機半導体であるα－ＮＰＤと、含フッ素重合体と、を共蒸着し、１００ｎｍの共蒸着膜を成膜して、屈折率測定用試料を得た。２つの材料の合計の蒸着速度は０．２ｎｍ／秒とした。蒸着速度を調整し、共蒸着膜におけるα－ＮＰＤと含フッ素重合体の体積比を所望の比率とした。 <Evaluation 2: Refractive index>
[Preparation of sample for refractive index measurement]
An organic semiconductor α-NPD and a fluorine-containing polymer were co-deposited on a silicon substrate to form a 100 nm co-deposited film to obtain a sample for refractive index measurement. The total deposition rate of the two materials was 0.2 nm / sec. The vapor deposition rate was adjusted so that the volume ratio of α-NPD to the fluorine-containing polymer in the co-deposited film was set to a desired ratio.
［屈折率の測定］
　多入射角分光エリプソメトリー（ジェー・エー・ウーラム社製：Ｍ－２０００Ｕ）を用いて、シリコン基板上の膜に対して、光の入射角を４５～７５度の範囲で５度ずつ変えて測定を行った。それぞれの角度において、波長４５０～８００ｎｍの範囲で約１．６ｎｍおきにエリプソメトリーパラメータであるΨとΔを測定した。前記の測定データを用い、有機半導体の誘電関数をＣａｕｃｈｙモデルによりフィッティング解析を行い、波長６００ｎｍの光に対する蒸着膜の屈折率を得た。 [Measurement of refractive index]
Using multi-incident angle spectroscopic ellipsometry (manufactured by JA Woolam Co., Ltd .: M-2000U), the incident angle of light is changed by 5 degrees in the range of 45 to 75 degrees with respect to the film on the silicon substrate. Was done. At each angle, ellipsometry parameters Ψ and Δ were measured at wavelengths in the range of 450-800 nm at intervals of approximately 1.6 nm. Using the above measurement data, the dielectric function of the organic semiconductor was subjected to fitting analysis by the Cauchy model to obtain the refractive index of the vapor-deposited film with respect to light having a wavelength of 600 nm.
＜評価３：ヘイズ＞
［ヘイズ測定用試料の作製］
　ガラス基板上に、α－ＮＰＤと、含フッ素重合体と、を共蒸着し、１００ｎｍの共蒸着膜を成膜して、ヘイズ測定用試料を得た。２つの材料の合計の蒸着速度は０．２ｎｍ／秒とした。蒸着速度を調整し、共蒸着膜におけるα－ＮＰＤと含フッ素重合体の体積比を所望の比率とした。 <Evaluation 3: Haze>
[Preparation of sample for haze measurement]
Α-NPD and a fluorine-containing polymer were co-deposited on a glass substrate to form a 100 nm co-deposited film to obtain a sample for haze measurement. The total deposition rate of the two materials was 0.2 nm / sec. The vapor deposition rate was adjusted so that the volume ratio of α-NPD to the fluorine-containing polymer in the co-deposited film was set to a desired ratio.
［ヘイズ測定］
　ヘイズ測定は、ヘイズメーター（東洋精機社製、ヘイズガードＫ５０－２９０）を用いて行った。
　ヘイズ測定用試料の初期ヘイズを測定後、試料を１００℃に熱したホットプレート上で１時間加熱した。試料を常温に戻した後に、再度ヘイズを測定した。さらに、試料を１２０℃に熱したホットプレート上で１時間加熱し、同様にしてヘイズを測定した。 [Haze measurement]
The haze measurement was performed using a haze meter (Haze Guard K50-290, manufactured by Toyo Seiki Co., Ltd.).
After measuring the initial haze of the haze measurement sample, the sample was heated on a hot plate heated to 100 ° C. for 1 hour. After returning the sample to room temperature, the haze was measured again. Further, the sample was heated on a hot plate heated to 120 ° C. for 1 hour, and the haze was measured in the same manner.
　得られたヘイズについて、以下のように評価した。
　〇：０．２未満
　△：０．２以上０．５未満
　×：０．５以上 The obtained haze was evaluated as follows.
〇: Less than 0.2 Δ: 0.2 or more and less than 0.5 ×: 0.5 or more
＜評価４：耐熱性１＞
［導電性評価用の素子１の作製］
　２ｍｍ幅の帯状にＩＴＯ(酸化インジウムスズ）が成膜されたガラス基板を用いた。
　当該基板を中性洗剤、アセトン、イソプロパノールを用いて超音波洗浄し、さらにイソプロパノール中で煮沸洗浄した上で、オゾン処理によりＩＴＯ膜表面の付着物を除去した。
　洗浄後の基板を真空蒸着機内に置き、圧力１０－４Ｐａ以下に減圧した上で、基板上に三酸化モリブデンを蒸着した。蒸着速度は０．１ｎｍ／秒であり、５ｎｍ成膜して正孔注入層を作製した。 <Evaluation 4: Heat resistance 1>
[Manufacturing of element 1 for conducting conductivity evaluation]
A glass substrate on which ITO (indium tin oxide) was formed into a strip having a width of 2 mm was used.
The substrate was ultrasonically cleaned with a neutral detergent, acetone, and isopropanol, and then boiled and washed in isopropanol, and then the deposits on the surface of the ITO film were removed by ozone treatment.
The washed substrate was placed in a vacuum vapor deposition machine, the pressure was reduced to 10 -4 Pa or less, and molybdenum trioxide was vapor-deposited on the substrate. The vapor deposition rate was 0.1 nm / sec, and a 5 nm film was formed to prepare a hole injection layer.
　次いで、正孔注入層上にα－ＮＰＤと、含フッ素重合体と、を共蒸着した。２つの材料の合計の蒸着速度は０．２ｎｍ／秒であり、１００ｎｍ成膜して電荷輸送層を作製した。蒸着速度を調整し、電荷輸送層におけるα－ＮＰＤと含フッ素重合体の体積比を所望の比率とした。
　次いで、電荷輸送層上に２ｍｍ幅の帯状にアルミニウムを蒸着した。帯状のアルミニウム膜は、基板の垂直方向から見た視野においてＩＴＯ膜と直交させた。これにより、素子面積４ｍｍ２（＝ＩＴＯ膜２ｍｍ×アルミニウム膜２ｍｍ）の導電性評価用の素子１を得た。 Next, α-NPD and a fluorine-containing polymer were co-deposited on the hole injection layer. The total vapor deposition rate of the two materials was 0.2 nm / sec, and a 100 nm film was formed to prepare a charge transport layer. The vapor deposition rate was adjusted so that the volume ratio of α-NPD to the fluorine-containing polymer in the charge transport layer was set to a desired ratio.
Next, aluminum was deposited on the charge transport layer in the form of a strip having a width of 2 mm. The strip-shaped aluminum film was orthogonal to the ITO film in the field of view seen from the vertical direction of the substrate. As a result, an element 1 for evaluating conductivity having an element area of 4 mm 2 (= ITO film 2 mm × aluminum film 2 mm) was obtained.
［素子１の耐熱性評価］
　ソースメータ（アジレント・テクノロジー社製：Ｂ１５００Ａ）を用い、素子１のＩＴＯを陽極、アルミニウムを陰極として電圧を印加しながら電圧を変化させ、電圧毎に素子に流れる電流を測定し、電界（Ｅ）（単位：ＭＶ／ｃｍ）に対する電流密度（Ｊ）（単位：ｍＡ／ｃｍ２）を求めた。 [Evaluation of heat resistance of element 1]
Using a source meter (Agilent Technology Co., Ltd .: B1500A), the voltage is changed while applying a voltage using ITO of element 1 as an anode and aluminum as a cathode, and the current flowing through the element is measured for each voltage to measure the electric field (E). The current density (J) (unit: mA / cm 2 ) with respect to (unit: MV / cm) was determined.
　次いで、Ｎ２雰囲気において、素子１を８０℃のホットプレート上で６０分加熱した。素子１を常温に戻した後、再度素子に流れる電流を測定し、電界（Ｅ）（単位：ＭＶ／ｃｍ）に対する電流密度（Ｊ）（単位：ｍＡ／ｃｍ２）を求めた。 Then, the N 2 atmosphere and heated 60 minutes element 1 at 80 ° C. on a hot plate. After returning the element 1 to room temperature, the current flowing through the element was measured again to obtain the current density (J) (unit: mA / cm 2) with respect to the electric field (E) (unit: MV / cm).
　次いで、Ｎ２雰囲気において、同じ素子１を９０℃のホットプレート上で６０分加熱した。素子１を常温に戻した後、再度素子に流れる電流を測定し、電界（Ｅ）（単位：ＭＶ／ｃｍ）に対する電流密度（Ｊ）（単位：ｍＡ／ｃｍ２）を求めた。 Then, the N 2 atmosphere, and the same element 1 is heated 60 minutes at 90 ° C. on a hot plate. After returning the element 1 to room temperature, the current flowing through the element was measured again to obtain the current density (J) (unit: mA / cm 2) with respect to the electric field (E) (unit: MV / cm).
　得られた結果から、素子１の耐熱性を以下のように評価した。
　×：８０℃に加熱後、０．４ＭＶ／ｃｍの電流密度が初期の９０％未満
　△：９０℃に加熱後、０．４ＭＶ／ｃｍの電流密度が初期の９０％未満
　〇：９０℃に加熱後、０．４ＭＶ／ｃｍの電流密度が初期の９０％以上 From the obtained results, the heat resistance of the element 1 was evaluated as follows.
×: After heating to 80 ° C, the current density of 0.4 MV / cm is less than 90% of the initial value Δ: After heating to 90 ° C, the current density of 0.4 MV / cm is less than 90% of the initial value 〇: Heating to 90 ° C. After that, the current density of 0.4 MV / cm is 90% or more of the initial value.
＜評価５：耐熱性２＞
［導電性評価用の素子２の作製］
　三酸化モリブデンの代わりにＨＡＴ－ＣＮ，α－ＮＰＤの代わりにＨＴ２１１を用いたこと以外は、［導電性評価用の素子１の作製］と同様に行い、導電性評価用の素子２を作製した。 <Evaluation 5: Heat resistance 2>
[Manufacturing of element 2 for conducting conductivity evaluation]
Except for the fact that HAT-CN was used instead of molybdenum trioxide and HT211 was used instead of α-NPD, the same procedure as [Preparation of element 1 for conductivity evaluation] was carried out to prepare element 2 for conductivity evaluation. ..
［素子２の耐熱性評価］
　加熱温度を１００℃、１１０℃、１２０℃、１３０℃とし、加熱時間をそれぞれ１５分間とした以外は［素子１の耐熱性評価］と同様に行い、電界（Ｅ）（単位：ＭＶ／ｃｍ）に対する電流密度（Ｊ）（単位：ｍＡ／ｃｍ２）を求めた。 [Evaluation of heat resistance of element 2]
The heating temperature was set to 100 ° C., 110 ° C., 120 ° C., and 130 ° C., and the heating time was set to 15 minutes, respectively. The current density (J) (unit: mA / cm 2 ) was determined.
　得られた結果から、素子２の耐熱性を以下のように評価した。
　×：１００℃に加熱後、０．４ＭＶ／ｃｍの電流密度が初期の９０％未満
　△：１１０℃に加熱後、０．４ＭＶ／ｃｍの電流密度が初期の９０％未満
　〇：１２０℃に加熱後、０．４ＭＶ／ｃｍの電流密度が初期の９０％未満
　〇〇：１３０℃に加熱後、０．４ＭＶ／ｃｍの電流密度が初期の９０％未満
　〇〇〇：１３０℃に加熱後、０．４ＭＶ／ｃｍの電流密度が初期の９０％以上 From the obtained results, the heat resistance of the element 2 was evaluated as follows.
×: After heating to 100 ° C, the current density of 0.4 MV / cm is less than 90% of the initial value Δ: After heating to 110 ° C, the current density of 0.4 MV / cm is less than 90% of the initial value 〇: Heating to 120 ° C. After, the current density of 0.4 MV / cm is less than 90% of the initial value 〇 〇: After heating to 130 ° C, the current density of 0.4 MV / cm is less than 90% of the initial value 〇 〇 〇: After heating to 130 ° C, 0 .4 MV / cm current density is 90% or more of the initial value
　以下の例１～１８において、含フッ素重合体の具体的な評価内容を説明する。 Specific evaluation contents of the fluorine-containing polymer will be described in Examples 1 to 18 below.
［例１］
　含フッ素重合体Ａ１を用い、上述の評価１～評価３、５を行った。
　評価２、評価３、評価５の試料作製では、有機半導体と含フッ素重合体の共蒸着において蒸着速度を調整し、有機半導体と含フッ素重合体との体積比を５０：５０とした。 [Example 1]
Evaluations 1 to 3 and 5 described above were carried out using the fluorine-containing polymer A1.
In the sample preparations of Evaluation 2, Evaluation 3, and Evaluation 5, the vapor deposition rate was adjusted in the co-evaporation of the organic semiconductor and the fluorine-containing polymer, and the volume ratio of the organic semiconductor and the fluorine-containing polymer was set to 50:50.
［例２］
　試料作製において、蒸着速度を調整し、有機半導体と含フッ素重合体の体積比を８０：２０とした以外は、例１と同様にして評価を行った。 [Example 2]
In the sample preparation, the evaluation was carried out in the same manner as in Example 1 except that the vapor deposition rate was adjusted and the volume ratio of the organic semiconductor to the fluorine-containing polymer was 80:20.
［例３］
　試料作製において蒸着速度を調整し、有機半導体と含フッ素重合体の体積比を２０：８０とした以外は、例１と同様にして評価を行った。 [Example 3]
The evaluation was carried out in the same manner as in Example 1 except that the vapor deposition rate was adjusted in the sample preparation and the volume ratio of the organic semiconductor to the fluorine-containing polymer was set to 20:80.
［例４］
　含フッ素重合体Ｂ１を用い、上述の評価１～評価５を行った。
　評価２～５の試料作製では、有機半導体と含フッ素重合体の共蒸着において蒸着速度を調整し、有機半導体と含フッ素重合体の体積比を５０：５０とした。 [Example 4]
Evaluations 1 to 5 described above were carried out using the fluorine-containing polymer B1.
In the sample preparation of evaluations 2 to 5, the vapor deposition rate was adjusted in the co-evaporation of the organic semiconductor and the fluorine-containing polymer, and the volume ratio of the organic semiconductor and the fluorine-containing polymer was set to 50:50.
［例５］
　含フッ素重合体としてＢ２を用いた以外は、例１と同様にして評価を行った。
［例６］
　含フッ素重合体としてＣ１を用いた以外は、例１と同様にして評価を行った。
［例７］
　含フッ素重合体としてＤ１を用いた以外は、例４と同様にして評価を行った。
［例８］
　含フッ素重合体としてＥ１を用いた以外は、例１と同様にして評価を行った。
［例９］
　含フッ素重合体としてＦ１を用いた以外は、例１と同様にして評価を行った。 [Example 5]
The evaluation was carried out in the same manner as in Example 1 except that B2 was used as the fluorine-containing polymer.
[Example 6]
The evaluation was carried out in the same manner as in Example 1 except that C1 was used as the fluorine-containing polymer.
[Example 7]
The evaluation was carried out in the same manner as in Example 4 except that D1 was used as the fluorine-containing polymer.
[Example 8]
The evaluation was carried out in the same manner as in Example 1 except that E1 was used as the fluorine-containing polymer.
[Example 9]
The evaluation was carried out in the same manner as in Example 1 except that F1 was used as the fluorine-containing polymer.
［例１０］
　含フッ素重合体としてＧ１を用いた以外は、例１と同様にして評価を行った。
［例１１］
　含フッ素重合体としてＪ１を用いた以外は、例１と同様にして評価を行った。
［例１２］
　含フッ素重合体としてＨ１を用いた以外は、例４と同様にして評価を行った。
［例１３］
　含フッ素重合体としてＢを用いた以外は、例１と同様にして評価を行った。
［例１４］
　含フッ素重合体としてＨを用いた以外は、例１と同様にして評価を行った。 [Example 10]
The evaluation was carried out in the same manner as in Example 1 except that G1 was used as the fluorine-containing polymer.
[Example 11]
The evaluation was carried out in the same manner as in Example 1 except that J1 was used as the fluorine-containing polymer.
[Example 12]
The evaluation was carried out in the same manner as in Example 4 except that H1 was used as the fluorine-containing polymer.
[Example 13]
The evaluation was carried out in the same manner as in Example 1 except that B was used as the fluorine-containing polymer.
[Example 14]
The evaluation was carried out in the same manner as in Example 1 except that H was used as the fluorine-containing polymer.
［例１５］
　含フッ素重合体Ｉ１を用い、評価１～４を行った。
　評価２～４の試料作製では、有機半導体と含フッ素重合体の共蒸着において蒸着速度を調整し、有機半導体と含フッ素重合体の体積比を５０：５０とした。 [Example 15]
Evaluations 1 to 4 were performed using the fluorine-containing polymer I1.
In the sample preparation of evaluations 2 to 4, the vapor deposition rate was adjusted in the co-evaporation of the organic semiconductor and the fluorine-containing polymer, and the volume ratio of the organic semiconductor and the fluorine-containing polymer was set to 50:50.
［例１６］
　市販の含フッ素重合体であるＦｌｕｏｎ ＰＦＡを用い、評価１：蒸着時のチャンバー圧変化を評価した。
　評価１にて蒸着時のチャンバー内上昇が著しく大きかったため、共蒸着を要する他の評価は行わなかった。 [Example 16]
Using a commercially available fluorine-containing polymer, Fluon PTFE, evaluation 1: change in chamber pressure during vapor deposition was evaluated.
In Evaluation 1, the rise in the chamber during vapor deposition was extremely large, so no other evaluation requiring co-deposition was performed.
［例１７］
　含フッ素重合体を用いない例として、α－ＮＰＤの単膜を蒸着速度０．１ｎｍ／秒で成膜した試料を用い、上述の評価２～４を行った。 [Example 17]
As an example in which the fluorine-containing polymer was not used, evaluations 2 to 4 described above were carried out using a sample in which a single film of α-NPD was formed at a vapor deposition rate of 0.1 nm / sec.
［例１８］
　含フッ素重合体を用いない例として、ＨＴ２１１の単膜を蒸着速度０．１ｎｍ／秒で成膜した試料を用い、評価５を行った。 [Example 18]
As an example in which the fluorine-containing polymer was not used, evaluation 5 was performed using a sample in which a single film of HT211 was formed at a vapor deposition rate of 0.1 nm / sec.
　上記例１～１８において、例１～１１が実施例に該当し、例１２～１８が比較例に該当する。結果を表２に示す。 In Examples 1 to 18, Examples 1 to 11 correspond to Examples, and Examples 12 to 18 correspond to Comparative Examples. The results are shown in Table 2.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　評価の結果、例１～１１においては、蒸着時のチャンバー内圧上昇が無く、安定した蒸着が可能であることが分かった。
　また、例１～１１は、加熱してもヘイズ上昇が抑制されていることが分かった。
　また、例１～１１の素子１，２は、耐熱性に優れていることが分かった。
　対して、例１３，１４，１６においては、蒸着時のチャンバー内圧上昇が認められ、蒸着状態が不安定になるおそれがあることが分かった。
　また、例１２，１４，１５および１７においては、加熱することでヘイズが上昇することが分かった。例１７では、加熱によりα－ＮＰＤが融解し、その後結晶化が進んだことにより散乱源が生じたと考えられる。例１２、１４、１５では、加熱により、共蒸着膜のナノドメイン構造が変化し、共蒸着膜の内部に散乱源が生じたと考えられる。
　また、例１２，１４，１５においては、素子１，２の耐熱性が低いことが分かった。
　以上の結果より、本発明が有用であることが確認できた。
　なお、２０２０年０２月２６日に出願された日本特許出願２０２０－０３０４６０号の明細書、特許請求の範囲、要約書および図面の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。 As a result of the evaluation, it was found that in Examples 1 to 11, stable vapor deposition was possible without an increase in the chamber internal pressure during vapor deposition.
Further, in Examples 1 to 11, it was found that the increase in haze was suppressed even when heated.
Further, it was found that the elements 1 and 2 of Examples 1 to 11 are excellent in heat resistance.
On the other hand, in Examples 13, 14 and 16, it was found that an increase in the chamber internal pressure during vapor deposition was observed, and the vapor deposition state may become unstable.
Further, in Examples 12, 14, 15 and 17, it was found that the haze was increased by heating. In Example 17, it is considered that α-NPD was melted by heating and then crystallization proceeded to generate a scattering source. In Examples 12, 14 and 15, it is considered that the nanodomain structure of the co-deposited film was changed by heating and a scattering source was generated inside the co-deposited film.
Further, in Examples 12, 14 and 15, it was found that the heat resistance of the elements 1 and 2 was low.
From the above results, it was confirmed that the present invention is useful.
The entire contents of the specification, claims, abstract and drawings of Japanese Patent Application No. 2020-030460 filed on February 26, 2020 are cited here as disclosure of the specification of the present invention. It is something to incorporate.
　１０…膜、５０…基板、５１，５２…蒸着源、５１ａ…有機半導体、５１ｂ…（有機半導体の）ドメイン、５２ａ…含フッ素重合体、５２ｂ…（含フッ素重合体の）ドメイン、１００，２００…有機ＥＬ素子（有機光電子素子）、１１０，２１０…基板、１１１…陽極、１１２…正孔注入層、１１３…正孔輸送層、１１４…発光層、１１５…電子輸送層、１１６…電子注入層、１１７，２１７…陰極、５００…チャンバー 10 ... film, 50 ... substrate, 51, 52 ... vapor deposition source, 51a ... organic semiconductor, 51b ... domain (of organic semiconductor), 52a ... fluorine-containing polymer, 52b ... domain (of fluorine-containing polymer), 100,200 … Organic EL element (organic photoelectron device), 110, 210… substrate, 111… anode, 112… hole injection layer, 113… hole transport layer, 114… light emitting layer, 115… electron transport layer, 116… electron injection layer , 117, 217 ... cathode, 500 ... chamber

Claims (15)

  1. 　下記（１）～（３）を満たす含フッ素重合体。
    （１）融点が２００℃以上である。
    （２）１×１０－３Ｐａの圧力下において昇温速度２℃／分で昇温させたときの熱重量減少率が、４００℃以下で実質的に１００％に達する。
    （３）１×１０－３Ｐａの圧力下において昇温速度２℃／分で昇温させたとき、熱重量減少率が１０％となる温度から９０％になる温度までの温度幅が１００℃以内である。     A fluorine-containing polymer that satisfies the following (1) to (3).
    (1) The melting point is 200 ° C. or higher.
    (2) The thermogravimetric reduction rate when the temperature is raised at a heating rate of 2 ° C./min under a pressure of 1 × 10 -3 Pa reaches substantially 100% at 400 ° C. or lower.
    (3) When the temperature is raised at a heating rate of 2 ° C./min under a pressure of 1 × 10 -3 Pa, the temperature range from the temperature at which the thermogravimetric reduction rate is 10% to the temperature at which the temperature is 90% is 100 ° C. Within.
  2. 　２５℃における貯蔵弾性率が１×１０７Ｐａ以上であり、
    　降温速度２℃／分で降温させたときに変化する貯蔵弾性率が１×１０６Ｐａ未満になる温度は１２０℃以上である、請求項１に記載の含フッ素重合体。     And the storage modulus 1 × 10 7 Pa or more at 25 ° C.,
    The fluorine-containing polymer according to claim 1, wherein the temperature at which the storage elastic modulus that changes when the temperature is lowered at a temperature lowering rate of 2 ° C./min is less than 1 × 10 6 Pa is 120 ° C. or higher.
  3. 　フルオロオレフィンに由来する単位を有する、請求項１または２に記載の含フッ素重合体。 The fluorine-containing polymer according to claim 1 or 2, which has a unit derived from a fluoroolefin.
  4. 　少なくともテトラフルオロエチレンに由来する単位を有する、請求項３に記載の含フッ素重合体。 The fluorine-containing polymer according to claim 3, which has at least a unit derived from tetrafluoroethylene.
  5. 　ペルフルオロアルキルビニルエーテルに由来する単位を有する、請求項３または４に記載の含フッ素重合体。 The fluorine-containing polymer according to claim 3 or 4, which has a unit derived from perfluoroalkyl vinyl ether.
  6. 　前記ペルフルオロアルキルビニルエーテルがペルフルオロプロピルビニルエーテルである、請求項５に記載の含フッ素重合体。 The fluorine-containing polymer according to claim 5, wherein the perfluoroalkyl vinyl ether is a perfluoropropyl vinyl ether.
  7. 　請求項１から６のいずれか１項に記載の含フッ素重合体と有機半導体とを含む膜。 A film containing the fluorine-containing polymer according to any one of claims 1 to 6 and an organic semiconductor.
  8. 　前記含フッ素重合体と前記有機半導体との合計に対する前記含フッ素重合体の割合が、２０～８０体積％である、請求項７に記載の膜。 The film according to claim 7, wherein the ratio of the fluorine-containing polymer to the total of the fluorine-containing polymer and the organic semiconductor is 20 to 80% by volume.
  9. 　ドーパントをさらに含む、請求項７または８に記載の膜。 The film according to claim 7 or 8, further comprising a dopant.
  10. 　前記含フッ素重合体と前記有機半導体との共蒸着膜である、請求項７から９のいずれか１項に記載の膜。 The film according to any one of claims 7 to 9, which is a co-deposited film of the fluorine-containing polymer and the organic semiconductor.
  11. 　請求項１から６のいずれか１項に記載の含フッ素重合体と有機半導体とを共蒸着させる工程を有する、膜の製造方法。 A method for producing a film, which comprises a step of co-depositing the fluorine-containing polymer according to any one of claims 1 to 6 and an organic semiconductor.
  12. 　前記共蒸着させる工程において、ドーパントをあわせて共蒸着させる、請求項１１に記載の膜の製造方法。 The method for producing a film according to claim 11, wherein in the step of co-depositing, a dopant is also co-deposited.
  13. 　請求項７から１０のいずれか１項に記載の膜を含む有機光電子素子。 An organic photoelectronic device including the film according to any one of claims 7 to 10.
  14. 　基板と、
    　前記基板に設けられた陽極と、
    　前記陽極に対向する陰極と、
    　前記陽極と前記陰極との間に配置された活性層と、
    　前記活性層と前記陽極との間に配置された正孔輸送層と、
    　前記正孔輸送層と前記陽極との間に配置された正孔注入層と、を備え、
    　前記正孔輸送層および前記正孔注入層の少なくとも一方の層が前記膜である、請求項１３に記載の有機光電子素子。     With the board
    The anode provided on the substrate and
    With the cathode facing the anode,
    An active layer arranged between the anode and the cathode,
    A hole transport layer arranged between the active layer and the anode,
    A hole injection layer arranged between the hole transport layer and the anode is provided.
    The organic photoelectron device according to claim 13, wherein at least one of the hole transport layer and the hole injection layer is the film.
  15. 　基板と、
    　前記基板に設けられた陽極と、
    　前記陽極に対向する陰極と、
    　前記陽極と前記陰極との間に配置された活性層と、
    　前記活性層と前記陰極との間に配置された電子輸送層と、
    　前記電子輸送層と前記陰極との間に配置された電子注入層と、を備え、
    　前記電子輸送層および前記電子注入層の少なくとも一方の層が前記膜である、請求項１３または１４に記載の有機光電子素子。     With the board
    The anode provided on the substrate and
    With the cathode facing the anode,
    An active layer arranged between the anode and the cathode,
    An electron transport layer arranged between the active layer and the cathode,
    An electron injection layer arranged between the electron transport layer and the cathode is provided.
    The organic photoelectron device according to claim 13 or 14, wherein at least one of the electron transport layer and the electron injection layer is the film.
PCT/JP2021/006902 2020-02-26 2021-02-24 Fluorine-containing polymer, film, film manufacturing method, and organic opto-electronic element WO2021172369A1 (en)

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